Hydroprocessing Bulk Catalyst and Uses Thereof

ABSTRACT

An improved hydroprocessing catalyst having improved morphology/dispersion characteristics is provided. The hydroprocessing catalyst has the formula (M t ) a (L u ) b (S v ) d (C w ) e (H x ) f (O y ) g (N z ) h , wherein M is at least one group VIB metal; L is optional and if present, L is at least one Group VIII non-noble metal; t, u, v, w, x, y, z representing the total charge for each of the components (M, X, S, C, H, O and N, respectively); ta+ub+vd+we+xf+yg+zh=0; 0=&lt;b and 0=&lt;b/a=&lt;5, (a+0.5 b )&lt;=d&lt;=(5 a +2 b ), 0&lt;=e&lt;=11( a +b), 0&lt;=f&lt;=7( a+b ), 0&lt;=g&lt;=5( a+b ), 0&lt;=h&lt;=0.5( a+b ). The catalyst is prepared by a process in which at least a sulfur additive is added to the sulfidation process in forming the catalyst precursor.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit under 35 USC 119 of U.S. ProvisionalPatent Application Nos. 60/984,323 and 60/984,290, all with a filingdate of Oct. 31, 2007. This application is a CIP of and claims priorityto U.S. patent application Ser. No. 11/933,085 filed Oct. 31, 2007. Thisapplication is also a CIP of and claims priority to U.S. patentapplication Ser. No. 12/168,687 filed Jul. 7, 2008, which is acontinuation of U.S. patent application Ser. No. 11/627,593 filed Jan.26, 2007, now U.S. Pat. No. 7,396,799, which is a continuation-in-partof U.S. patent application Ser. No. 10/938,003 filed Sep. 10, 2004,abandoned.

TECHNICAL FIELD

The invention relates generally to bulk catalysts for use in theconversion of heavy oils and residua and methods for making thereof.

BACKGROUND

The petroleum industry is increasingly turning to heavy crudes, resids,coals and tar sands as sources for feedstocks. Feedstocks derived fromthese heavy materials contain more sulfur and nitrogen than feedstocksderived from more conventional crude oils, requiring a considerableamount of upgrading in order to obtain usable products therefrom. Theupgrading or refining generally being accomplished by hydrotreatingprocesses, i.e., treating with hydrogen of various hydrocarbonfractions, or whole heavy feeds, or feedstocks, in the presence ofhydrotreating catalysts to effect conversion of at least a portion ofthe feeds, or feedstocks to lower molecular weight hydrocarbons, or toeffect the removal of unwanted components, or compounds, or theirconversion to innocuous or less undesirable compounds.

Catalyst precursors commonly used for these hydrotreating reactionsinclude materials such as cobalt molybdate on alumina, nickel onalumina, cobalt molybdate promoted with nickel, nickel tungstate, etc.U.S. Pat. Nos. 4,824,821 and 5,484,755 and US Patent Publication No.2006/0054535 disclose hydroprocessing catalysts in the form of highactivity slurry. The slurry catalyst is produced from group VIB metalcompounds by sulfiding an aqueous mixture of the metal compound withhydrogen sulfide (H₂S) gas at a pressure of up to 5,000 psi (340 atm).

US Patent Publication No. 20070161505 discloses an ultra-dispersedcatalyst composition having a median particle diameter between 30-6000nm, prepared by mixing separate micro-emulsions of Group VIB or VIIIBnon-noble metals. Each micro-emulsion is prepared by mixing solutionscontaining either Group VIB or VIIIB metal with a hydrocarbon feedstock.As the metals were sulfided separately, when the micro-emulsions aremixed together, a first metal component (e.g., NiS) simply deposits onthe outer layer of the second metal component (e.g., MOS₂), thus forminga “core shell” type catalyst structure. Core-shell type catalysts formedwith pre-sulfided metal components have lower catalytic activity thancatalysts formed in a process wherein the metals are allowed to react/incontact with each other prior to sulfidation to form a more homogeneousstructure.

In the preparation of a bulk slurry type catalyst, it is desirable toincrease the incorporation of sulfur in the catalyst precursor in thesulfidation step.

The invention relates to an improved process to prepare bulk catalystsfor use in the conversion of heavy oils and residua, wherein sulfuradditives are used.

SUMMARY OF THE INVENTION

In one aspect, this invention relates to a hydroprocessing catalystcomposition having a formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),wherein M is at least one group VIB metal; L (“Promoter Metal”) isoptional. If present, L is at least one of a non-noble Group VIII metal,a Group VIIIB metal, a Group VIB metal, a Group IVB metal, and a GroupIIB metal; t, u, v, w, x, y, z, each representing total charge for eachof: M, L, S, C, H, O and N, respectively; ta+ub+vd+we+xf+yg+zh=0;0=>b/a=>5, (a+0.5b)<=d<=(5a+2b), 0<=e<=11(a+b), 0<=f<=7(a+b),0<=g<=5(a+b), 0<=h<=0.5(a+b), wherein the catalyst has been prepared bya process comprising the steps of: combining and reacting M with X toobtain an intermediate mixture; sulfiding the intermediate mixture witha sulfiding agent in solution and at least a sulfur additive, forming acatalyst precursor; and mixing the catalyst precursor with a hydrocarboncompound to form the hydroprocessing catalyst composition.

In one aspect, the at least a sulfur additive is selected from the groupof thiadiazoles, thio acids, thio amides, thiocyanates, thio esters,thiophenols, thiosemicarbazides, thioureas, mercapto alcohols, dialkylsulfides, dihydroxyalkyl sulfides, diaryl sulfides, diaralkyl sulfides,dimethyl sulfoxides, diethanol disulfide, tert-nonylpolysulfides,dimethyl sulphide, dimethyl disulphide, 2,2-dithiobis ethanol, andmixtures thereof.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates the steps involved in an embodiment for preparing thecatalyst composition.

FIG. 2 illustrates a diagram of a process to prepare an embodiment ofthe catalyst composition in continuous mode.

FIG. 3 illustrates the steps involved in another embodiment forpreparing the catalyst composition, wherein at least a surfactant isadded to at least one of the process steps.

FIG. 4 illustrates the steps involved in another embodiment forpreparing the catalyst composition, wherein at least a surfactant isadded to at least one of the process steps.

FIG. 5 shows the powder X-ray diffraction pattern of an intermediatecatalyst precursor sample in one embodiment of the invention, showing acomplex mixture of poorly crystalline compounds with broad spectra,multiple diffraction peaks of low intensity in the PXRD spectrumindicating small crystallite size.

FIG. 6 is a PXRD spectrum of a comparative stock crystalline ammoniumtetrathiomolybdate.

FIG. 7 shows the powder X-ray diffraction pattern of a catalyst samplein one embodiment of the invention, showing poor crystallinity withdiffuse Bragg peaks (width of peaks at ½ height is >>1° in 2-thetascale).

FIG. 8 shows a PXRD spectrum of a comparative crystalline MoS₂ withwell-defined diffraction peaks of high intensity.

FIG. 9 shows volume-based particle size analysis of an embodiment of acatalyst compound of the invention.

FIG. 10 shows the powder X-ray diffraction pattern of the catalystsample prepared from Example 19, with the addition of a surfactant.

DETAILED DESCRIPTION

The following terms will be used throughout the specification and willhave the following meanings unless otherwise indicated.

As used here, the term “bulk catalyst” may be used interchangeably with“unsupported catalyst,” meaning that the catalyst composition is NOT ofthe conventional catalyst form which has a preformed, shaped catalystsupport which is then loaded with metals via impregnation or depositioncatalyst. In one embodiment, the bulk catalyst is formed throughprecipitation. In another embodiment, the bulk catalyst has a binderincorporated into the catalyst composition. In yet another embodiment,the bulk catalyst is formed from metal compounds and without any binder.In a fourth embodiment, the bulk catalyst is a dispersing-type catalyst(“slurry catalyst”) for use as dispersed catalyst particles in mixtureof liquid (e.g., hydrocarbon oil).

As used herein, the term “free of promoter metal” or “substantially freeof promoter metal” means that in the production of the bulk catalyst, nopromoter metal, e.g., group VIII metals in their elemental, compound, orionic form, will be added. Traces of group VIII promoter metals such asnickel can be present. Generally, however, the amount of group VIIImetals if any is less than 0.1 wt. % (of the total weight of the bulkcatalyst).

As used herein, “heavy oil” feed or feedstock refers to heavy andultra-heavy crudes, including but not limited to resids, coals, bitumen,tar sands, etc. Heavy oil feedstock may be liquid, semi-solid, and/orsolid. Examples of heavy oil feedstock that might be upgraded asdescribed herein include but are not limited to Canada Tar sands, vacuumresid from Brazilian Santos and Campos basins, Egyptian Gulf of Suez,Chad, Venezuelan Zulia, Malaysia, and Indonesia Sumatra. Other examplesof heavy oil feedstock include residuum left over from refineryprocesses, including “bottom of the barrel” and “residuum” (or“resid”)—atmospheric tower bottoms, which have a boiling point of atleast 343° C. (650° F.), or vacuum tower bottoms, which have a boilingpoint of at least 524° C. (975° F.), or “resid pitch” and “vacuumresidue”—which have a boiling point of 524° C. (975° F.) or greater.

Properties of heavy oil feedstock may include, but are not limited to:TAN of at least 0.1, at least 0.3, or at least 1; viscosity of at least10 cSt; API gravity at most 15 in one embodiment, and at most 10 inanother embodiment. A gram of heavy oil feedstock typically contains atleast 0.0001 grams of Ni/V/Fe; at least 0.005 grams of heteroatoms; atleast 0.01 grams of residue; at least 0.04 grams C5 asphaltenes; atleast 0.002 grams of MCR; per gram of crude; at least 0.00001 grams ofalkali metal salts of one or more organic acids; and at least 0.005grams of sulfur. In one embodiment, the heavy oil feedstock has a sulfurcontent of at least 5 wt. % and an API gravity ranging from −5 to +5. Aheavy oil feed comprises Athabasca bitumen (Canada) typically has atleast 50% by volume vacuum reside. A Boscan (Venezuala) heavy oil feedmay contain at least 64% by volume vacuum residue.

The terms “treatment,” “treated,” “upgrade”, “upgrading” and “upgraded”,when used in conjunction with a heavy oil feedstock, describes a heavyoil feedstock that is being or has been subjected to hydroprocessing, ora resulting material or crude product, having a reduction in themolecular weight of the heavy oil feedstock, a reduction in the boilingpoint range of the heavy oil feedstock, a reduction in the concentrationof asphaltenes, a reduction in the concentration of hydrocarbon freeradicals, and/or a reduction in the quantity of impurities, such assulfur, nitrogen, oxygen, halides, and metals.

The upgrade or treatment of heavy oil feeds is generally referred hereinas “hydroprocessing” (or hydroconversion). Hydroprocessing is meant asany process that is carried out in the presence of hydrogen, including,but not limited to, hydroconversion, hydrocracking, hydrogenation,hydrotreating, hydrodesulfurization, hydrodenitrogenation,hydrodemetallation, hydrodearomatization, hydroisomerization,hydrodewaxing and hydrocracking including selective hydrocracking. Theproducts of hydroprocessing may show improved viscosities, viscosityindices, saturates content, low temperature properties, volatilities anddepolarization, etc.

As used herein, hydrogen refers to hydrogen, and/or a compound orcompounds that when in the presence of a heavy oil feed and a catalystreact to provide hydrogen.

As used herein, the term “surfactant” (can be used interchangeably with“surface active agent,” “stabilizer, or “surface modifier”) refersgenerally to any material that operates to low the surface tension of aliquid, thus improving the wetting at the interface between thedispersed catalyst particles and the hydrocarbon oil. Alternatively orin combination, the surfactant operates to lower the surface tensionbetween the catalyst material in suspension and the solvent/solution inwhich the catalyst material is suspended, thus in one embodiment thesurfactant allows controlled and dispersed layering of the catalystparticles in the solution that contains the catalyst material.

As used herein, the term “catalyst precursor” refers to a compoundcontaining one or more catalytically active metals, from which compoundthe catalyst of the invention having the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C_(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),is eventually formed, and which compound may be catalytically active asa hydroprocessing catalyst.

As used herein, the phrase “one or more of” or “at least one of” whenused to preface several elements or classes of elements such as X, Y andZ or X₁-X_(n), Y₁-Y_(n) and Z₁-Z_(n), is intended to refer to a singleelement selected from X or Y or Z, a combination of elements selectedfrom the same common class (such as X₁ and X₂), as well as a combinationof elements selected from different classes (such as X₁, Y₂ and Z_(n)).

As used herein, “heavy oil” feed or feedstock refers to heavy andultra-heavy crudes, including but not limited to resids, coals, bitumen,tar sands, etc. Heavy oil feedstock may be liquid, semi-solid, and/orsolid.

SCF/BBL (or scf/bbl) refers to a unit of standard cubic foot of gas (N₂,H₂, etc.) per barrel of hydrocarbon feed.

The Periodic Table referred to herein is the Table approved by IUPAC andthe U.S. National Bureau of Standards, an example is the Periodic Tableof the Elements by Los Alamos National Laboratory's Chemistry Divisionof October 2001.

The term “Group VIII metal” refers to iron, cobalt, nickel, ruthenium,rhenium, palladium, osmium, iridium, platinum, and combinations thereofin their elemental, compound, or ionic form.

The term “Group VIB metal” refers to chromium, molybdenum, tungsten, andcombinations thereof in their elemental, compound, or ionic form.

Catalyst Formula: In one embodiment, the catalyst composition asexpressed in elemental form, is of the general formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h).The formula herein refers to the catalyst solids, constituting thecatalyst slurry in oil, prepared by the method described below. In theequation, M represents at least one group VIB metal, such as Mo, W, etc.or a combination thereof. L is optional and if present, functions as apromoter metal, representing at least one of: a non-noble Group VIIImetal such as Ni, Co; a Group VIIIB metal such as Fe; a Group VIB metalsuch as Cr; a Group IVB metal such as Ti; a Group IIB metal such as Zn,and combinations thereof (L is hereinafter referred to as “promotermetal”). Also in the equation, t, u, v, w, x, y, z representing thetotal charge for each of the component (M, L, S, C, H, O and N,respectively); ta+ub+vd+we+xf+yg+zh=0. The subscripts ratio of b to ahas a value of 0 to 5, and (0<=b/a<=5). S represents sulfur with thevalue of the subscript d ranging from (a+0.5b) to (5a+2b). C representscarbon with subscript e having a value of 0 to 11(a+b). H is hydrogenwith the value of f ranging from 0 to 7(a+b). O represents oxygen withthe value of g ranging from 0 to 5(a+b); and N represents nitrogen withh having a value of 0 to 0.5(a+b).

In one embodiment, the catalyst is without any promoter L, for b=0. Inanother embodiment with promoter metal L, a and b each are suitablygreater than 0 such that the ratio of a:b is in the range of 1:5 to10:1. For example, in one embodiment with b/a having a value of 0.2, ahas a value of 5 and b has a value of 1. Thus, at this b/a ratio of 0.2,(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h)would include compositions ranging from (M)₅(L)(S)_(5.5), including(M)₅(L)(S)_(5.5)(C)(H)(O)(N), to (M)₅(L)(S)₂₇(C)₆₆(H)₄₂(O)₃₀(N)₃.

In one embodiment, M is at least one or two metals selected fromchromium, molybdenum and tungsten. In a second embodiment, M is selectedfrom molybdenum, tungsten and a combination of the two. In yet anotherembodiment, M is molybdenum.

In one embodiment where both molybdenum and tungsten are used, thecatalyst is of the formula(Mo_(z)W_(1-z))_(a)(L)_(b)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h), where0<z<1. In yet another embodiment where M is a mixture of Mo and W, themolybdenum to tungsten ratio is in the range of 9:1-1:9.

In one embodiment, L is at least one or two non-noble metals selectedfrom nickel, cobalt and iron. In a second embodiment, L is selected fromnickel, cobalt and a combination of nickel and cobalt. In a thirdembodiment, L is nickel. In one embodiment where L is a mixture of twometals such as Ni and Co, the catalyst is of the formula(M)_(a)(Ni_(z)Co_(1-z))_(b)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h), where0<z<1. In another embodiment where L is a mixture of multiple metalssuch as Ni, Co, Fe, Zn, Cr, Ti, the catalyst is of the formula(M)_(a)(Ni_(z)Co_(z)Fe_(z″)Zn_(z*)Cr_(z*′)Ti_(z*″))_(b)(S)_(d)(C)_(e)(H)_(d)(O)_(g)(N)_(h),where 0≦z, z′, z″, z*, z*′, z*″ and (z+z′+z″+z*+z*′+z*″)=1.

In the sections that follow, the reference to “molybdenum” is by way ofexemplification only for component (M) in the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),and is not intended to exclude other Group VIB metals/compounds andmixtures of Group VIB metal/compounds represented by (M) in the catalystformula. Similarly, the reference to “nickel” is by way ofexemplification only for the component (L) in the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h);and is not meant to exclude other promoter metals, i.e., group VIIInon-noble metal components, Group VIIIB metals; Group VIB metals; GroupIVB metals; Group IIB metals and mixtures thereof that can be used inthe catalyst formula.

The sections that follow describe reagents that can be used in themanufacture(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h).The term reagent refers to a raw material that can be used in themanufacture of the catalyst, which can be in their elemental, compound,or ionic form.

As used herein, the term “metal” refers to reagents in their elemental,compound, or ionic form. Also as used herein, the term “metal” or “metalprecursor” in the singular form is not limited to a single metal ormetal precursor, i.e., Group VIB or promoter metals, but also includesthe plural references for mixtures of metals. As used herein, “in thesolute state” means that the metal component is in a protic liquid form.Also as used herein, the term “metal precursor” refers to the metalcompound feed to the process.

Group VIB Transition Metal/Precursor Component: In one embodiment, atleast part of the Group VIB transition (M) metal precursor is added inthe solid state. In a second embodiment, at least part of the group VIBmetal precursor is added in the solute state. In one embodiment, themolar ratio of Group VIB metal to promoter metal is in the range of9:1-1:9. In a second embodiment, the molar ratio is in the range of 3:1to 1:3.

In one embodiment, (M) metal precursor is selected from molybdenumand/or tungsten components, e.g., alkali metal or ammonium metallates ofmolybdenum, (e.g., ammonium molybdate and also iso-, peroxo-, di-, tri-,tetra-, hepta-, octa-, or tetradecamolybdate), ammonium salts ofphosphomolybdic acids, Mo—P heteropolyanion compounds, Wo—Siheteropolyanion compounds, W—P heteropolyanion compounds. W—Siheteropolyanion compounds, Ni—Mo—W heteropolyanion compounds. Co—Mo—Wheteropolyanion compounds, alkali metal or ammonium tungstates (alsometa-, para-, hexa-, or polytungstate), or mixtures thereof, added inthe solute state such as water-soluble molybdenum and tungstencompounds.

In one embodiment, the (M) metal precursor is selected from the group ofalkali metal or ammonium metallates of molybdenum in organic solventssuch as a normal alkane, hydrocarbons, or petroleum products such asdistillate fractions wherein the molybdenum compound is allowed tosubsequently decompose under pressure and temperature, prior to orconcurrent with the addition of the promoter metal precursor.

In yet another embodiment, the group VIB metal precursor is selectedfrom the group of alkali metal heptamolybdates, alkali metalorthomolybdates, alkali metal isomolybdates, phosphomolybdic acid, andmixtures thereof. In a fourth embodiment, it is selected from the groupof molybdenum (di- and tri) oxide, molybdenum carbide, molybdenumnitride, aluminum molybdate, molybdic acid (e.g. H₂MoO₄), or mixturesthereof. In a fifth embodiment, the group VIB metal compound is anorganometallic complex, e.g., oil soluble compound or complex oftransition metal and organic acid, selected from naphthenates,pentanedionates, octoates, acetates, and the like. Examples includemolybdenum naphthanate and molybdenum hexacarbonyl.

In one embodiment, the (M) precursor is a water-soluble ammoniumheptamolybdate [(NH₄)₆Mo₇O_(24*)4H₂O]. In another embodiment, it isammonium thiomolybdate. In yet another embodiment, it is a polyalkylthiomolybdate.

Promoter Metal Precursor: The promoter metal L is optional. In oneembodiment, the catalyst precursor is optionally promoted with at leasta metal component as promoter metal L. In one embodiment, the promotermetal (L) precursor is in a solute state, wherein the whole amount ofthe metal precursor is in a protic liquid form, and wherein the metal isat least partly present as a solid and partly dissolved in the proticliquid in one embodiment.

In one embodiment, the promoter metal (L) precursor is a metal salt ormixtures selected from nitrates, hydrated nitrates, chlorides, hydratedchlorides, sulfates, hydrated sulfates, formates, acetates,hypophosphites, and mixtures thereof, added in a solute state Examplesinclude water-soluble nickel and/or cobalt components, e.g.water-soluble nickel and/or cobalt salts such as nitrates, sulfates,acetates, chlorides, formates or mixtures thereof of nickel and/orcobalt as well as nickel hypophosphite.

In one embodiment, the promoter metal (L) metal precursor is awater-soluble nickel component, e.g. nickel nitrate, nickel sulfate,nickel acetate, nickel chloride, or mixtures thereof. In anotherembodiment, the metal precursor is a nickel compound which is at leastpartly in the solid state, e.g., a water-insoluble nickel compound suchas nickel carbonate, nickel hydroxide, nickel phosphate, nickelphosphite, nickel formiate, nickel sulfide, nickel molybdate, nickeltungstate, nickel oxide, nickel alloys such as nickel-molybdenum alloys,Raney nickel, or mixtures thereof. In a third embodiment, the metalprecursor containing (L) is a water-soluble nickel sulfate solution. Inyet another embodiment, promoter metal compound is added to thewater-soluble reagent, e.g., an iron component in the solute stateselected from iron acetate, chloride, formate, nitrate, sulfate andmixtures thereof.

In one embodiment, the promoter metal (L) precursor is a nickel sulfateaqueous solution.

Sulfiding Agent Component: In one embodiment, the sulfiding agent iselemental sulfur by itself. In another embodiment, the sulfiding agentis a sulfur-containing compound which under prevailing conditions, isdecomposable into hydrogen sulphide. In yet a third embodiment, thesulfiding agent is H₂S by itself or in H₂.

The sulfiding agent is present in an amount in excess of thestoichiometric amount required to form the catalyst. In anotherembodiment, the amount of sulfiding agent represents a sulfur to GroupVIB metal mole ratio of at least 3 to 1 to produce a sulfided catalystfrom the catalyst precursor. In a third embodiment, the total amount ofsulfur-containing compound is generally selected to correspond to any ofabout 50-300%, 70-200%, and 80-150%, of the stoichiometric sulfurquantity necessary to convert the metals into for example, CO₉S₈, MoS₂,WS₂, Ni₃S₂, etc.

In one embodiment, the sulfiding agent is selected from the group ofammonium sulfide, ammonium polysulfide ((NH₄)₂S₂), ammonium thiosulfate((NH₄)₂S₂O₃), sodium thiosulfate (Na₂S₂O₃), thiourea (CSN₂H₄), carbondisulfide (CS₂), dimethyl disulfide (DMDS), dimethyl sulfide (DMS),tertiarybutyl polysulfide (PSTB) and tertiarynonyl polysulfide (PSTN),and mixtures thereof. In another embodiment, the sulfiding agent isselected from alkali- and/or alkaline earth metal sulfides, alkali-and/or alkaline earth metal hydrogen sulfides, and mixtures thereof. Theuse of sulfiding agents containing alkali- and/or alkaline earth metalsmay require an additional separation process step to remove the alkali-and/or alkaline earth metals from the spent catalyst.

In one embodiment, the sulfiding agent is ammonium sulfide in aqueoussolution. An aqueous ammonium sulfide solution can be synthesized fromhydrogen sulfide and ammonia—common refinery off-gases. This synthesizedammonium sulfide is readily soluble in water and can easily be stored inaqueous solution in tanks prior to use. Since ammonium sulfide solutionis more dense than resid, it can be separated easily in a settler tankafter reaction.

Optional Component—Binder Material: In one embodiment, a binder isoptionally included in the process for making the catalyst. Generally,the binder material has less catalytic activity than the catalystcomposition (without the binder material) or no catalytic activity atall. Consequently, by adding a binder material, the activity of thecatalyst composition may be reduced. Therefore, the amount of bindermaterial to be added in the process generally depends on the desiredactivity of the final catalyst composition. Binder amounts from 0-95 wt.% of the total composition can be suitable, depending on the envisagedcatalytic application. In another embodiment, binder can be optionallyadded in the range of 0.5-75 wt. % of the total composition.

The binder materials can be added to the metal precursors eithersimultaneously or one after the other. Alternatively, the metalprecursors can be combined together and subsequently a binder materialcan be added to the combined metal precursors. It is also possible tocombine part of the metal precursors either simultaneously or one afterthe other, to subsequently add the binder material and to finally addthe rest of the metal precursors either simultaneously or one after theother. Furthermore, it is also possible to combine the binder with metalprecursors in the solute state and to subsequently add a metal precursorat least partly in the solid state.

In one embodiment, the binder material is mixed with a Group VIB metaland/or a promoter metal, e.g., a Group VIII non-noble metal, prior tobeing mixed with the bulk catalyst composition and/or prior to beingadded during the preparation thereof. Compositing the binder materialwith any of these metals in one embodiment is carried out byimpregnation of the solid binder with these materials.

Optional binder materials include any materials that are conventionallyapplied as a binder in hydroprocessing catalysts. Examples includesilica, silica-alumina, such as conventional silica-alumina,silica-coated alumina and alumina-coated silica, alumina such as(pseudo)boehmite, or gibbsite, titania, zirconia, cationic clays oranionic clays such as saponite, bentonite, kaoline, sepiolite orhydrotalcite, or mixtures thereof. In one embodiment, binder materialsare selected from silica, colloidal silica doped with aluminum,silica-alumina, alumina, titanium, zirconia, or mixtures thereof. In oneembodiment, the catalyst comprises a refractory oxide material whichcomprises 50 wt. % or more titania, on oxide basis.

These binders may be applied as such or after peptization. It is alsopossible to apply precursors of these binders that, during the processare converted into any of the above-described binders. Suitableprecursors are, e.g., alkali metal aluminates (to obtain an aluminabinder), water glass (to obtain a silica binder), a mixture of alkalimetal aluminates and water glass (to obtain a silica alumina binder), amixture of sources of a di-, tri-, and/or tetravalent metal such as amixture of water-soluble salts of magnesium, aluminum and/or silicon (toprepare a cationic clay and/or anionic clay), chlorohydrol, aluminumsulfate, or mixtures thereof.

In one embodiment with the incorporation of a binder or binders, thecatalyst is of the formula(M^(t))_(a)(L^(u))_(b)(Z)_(I)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),with Z representing titanium and optionally one or more elementsselected from aluminum, silicon, magnesium, zirconium, boron, and zinc.

In one embodiment where alumina is used as a binder, the alumina binderhas a surface area ranging from 100 to 400 m²/g, with a pore volumeranging from 0.5 to 1.5 ml/g measured by nitrogen adsorption. In oneembodiment where titania is used as a binder, the titania has an averageparticle size of less than 50 microns. In a second embodiment, thetitania binder has an average particle size of less than 5 microns. In athird embodiment, the titania binder has an average particle size ofgreater than 0.005 microns. In a fourth embodiment, the titania binderhas a BET surface area of 10 to 700 m²/g.

Sulfur Additive Component: The use of the sulfur additive is optional.In one embodiment, at least a sulfur additive (also referred to as“sulfiding additive”) is added in mixture with any of the sulfidingagents described above, the (M)-metal precursor, the (L)-metalprecursor, separately or in a mixture with all reagents. The role of thesulfur additive is to increase the incorporation of sulfur in thecatalyst in one embodiment, and in another embodiment, increasing thestability of the catalyst activities.

In one embodiment, the amount of sulfur additive (used interchangeablywith additives) ranges from 5 to 50 wt. % of the amount of sulfurintroduced in the catalyst (via the sulfiding agent). In a secondembodiment, this amount ranges from 10 to 40 wt. % of the amount ofsulfur introduced in the catalyst. In a third embodiment, from 15 to 30wt. %. The sulfur additive can be added either in the pure state ordissolved in a suitable solvent, e.g., water.

In one embodiment, the sulfur additive is selected from the group ofthiodiazoles, thio acids, thio amides, thiocyanates, thio esters,thiophenols, thiosemicarbazides, thioureas, and mixtures thereof.Examples include but are not limited to, thiobenzoic acid, 2-thiocresol,3-thiocresol, 4-thiocresol, 3,3′-thiodipropionic acid,3,3′-thiodipropionitrile, 2,3,6-trimethyl thiophenol, methylthioglycolate, 4-methyl-3-thiosemicarbazide, naphthalene-2-thiol, phenylisothiocyante, 2-phenyl thiophenol, thioacetamide, thiobenzamide,2,6-dimethyl thiophenol, 3,5-dimethyl thiophenol, 2,2′-dinitrodiphenyldisulfide, 2,5-dithiobiurea, ethyl thioglycolate, 2-methoxy thiophenol,3-methoxy thiophenol, 2-methyl-5-mercapto-1,3,4-thiadiazole,amidinothiourea, 2-amino-5-ethylthio-1,3,4-thiadiazole,2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole,2-amino thiophenol, benzene-1,3-dithiol, 3-chlorothiophenol and2,5-dimercapto-1,3,4-thiadiazole (D.M.T.D.).

In another embodiment, the sulfur additive is selected from the group ofmercapto alcohols. Examples are compounds of formula HS—CH₂—CH₂OH(2-mercaptoethanol) and HS—CH₂—C(C₆H₅) H—OH(1-mercapto-2-phenyl-2-ethanol). In yet another embodiment, the sulfuradditive is one of dialkyl sulfides (such as di-n-butyl sulfides,di-tert-butyl sulfides), dihydroxyalkyl sulfides (such as thiodiethyleneglycol (S(CH₂CH₂OH)₂), thiodipropylene glycol), diaryl sulfides (such asdiphenyl sulfide), diaralkyl sulfides (such as dibenzyl sulfide), alkylethers, thiophenols (such as thioanisole), cyclic thio ethers and theirsubstituted derivatives (such as ethylene sulfide, thiophene, thiazole,thiopyrone, thioxanthone, thioxanehydrol, 1,4-thioxane), dimethylsulfoxide, ethylthiol ethanol, thioglycolic acid, dithioglycol, anddiethanol disulfide.

In one embodiment, the sulfur additive is a commercially availablesulfur-containing compound, e.g., tert-nonylpolysulfide such as TPS-374from Atofina Company or catalyst presulfiding agent SulfiZol™ fromLubrizol Corp.

In another embodiment, the sulfur additive is sulphur in powder form(flowers of sulphur), which can be used in suspension either alone ormixed with another sulphur compound (e.g. an organic polysulphide) inexemplified weight proportions of 5 to 90% polysulphide and 95 to 10%elementary sulphur in one example, and 20 to 50% polysulphide and 80 to50% elementary sulphur in another example.

In another embodiment, the sulfur additive is selected from the group ofdimethyl sulphide DMS, dimethyl disulphide DMD, diethanol disulfide or2,2-dithiobis ethanol (DEODS) soluble in water, glycols, andpolyglycols. In one example, the sulfur additive is DEODS mixed informic acid or a methyl formate organic solution.

Surfactant Component: The use of a surfactant component is optional. Inone embodiment, a surfactant is used. The surfactant can be any suitablesurfactant which use favorably improves the bulk catalyst'scharacteristics, including its dispersion, metal surface area,morphology and the like, employed in an amount ranging from in an amountof 0.001 to 5 wt. %. In a second embodiment, the amount of surfactantranges from 0.005 to 3 wt. %. In a third embodiment, from 0.01 to 2 wt.%.

In one embodiment, the optional surfactant is added to the metalprecursor components either simultaneously or one after the other.Alternatively, the metal precursors can be combined together first andsubsequently the surfactant can be added to the combined metalprecursors. In another embodiment, the surfactant is added to thehydrocarbon transforming agent to enhance the micro-emulsion formation.In one embodiment, the amount of surfactant added to the hydrocarbontransforming agent ranges from 0.005 to 3 wt. %. In another embodiment,it ranges from 0.01 to 2 wt. %.

In yet one embodiment as known in the art, the surfactant can be addedto the feedstock to the hydroprocessing operation, e.g., a heavy oilfeed stream to be hydroconverted, instead of or in addition to theaddition of the surfactant to the hydrocarbon transforming agent. If thesurfactant is solely added to the hydroconversion feedstock, the amountto be added ranges from 0.001 to 0.05 wt. % of the feed in oneembodiment and 0.005 to 0.01 wt. % in a second embodiment. See work byEast China University of Science teaching the addition of enhancingadditives to facilitate the intensification of oil cracking, includingreducing the formation of coke on the catalyst and increasing the liquidyield by 1-2.8% (Acta Petrolei Sinica, Vol. 19, Issue 4, pp. 36-44, ISSN10018719). Also see work by Perm State Technical University teaching theuse of surfactants in the refining of oil distillates, with yieldincreases of 1.3-4.2% (Khimiya I Tekhnologiya Topilv I Masel, Issue 3,Year 1997, pp. 20-21, ISSN 00231169 and later publications by sameauthors).

The surfactant can be at least one of anionic surfactants, zwitterionicsurfactants, amphoteric surfactants, nonionic surfactants, cationicsurfactants, and combinations thereof. In one embodiment, the non-ionicsurfactant is selected from polyoxyethylenesorbitan monolaurate,polyoxyethylenated alkylphenols, polyoxyethylenated alkylphenolethoxylates, and the like. Suitable cationic surfactants includequarternary long-chain organic amine salts, quarternary polyethoxylatedlong-chain organic amine salts, and the like. In another embodiment, thesurfactant is selected from the group of solvent materials having a highsurface tension property such as ethylene carbonate, benzophenone;benzyl cyanide, nitrobenzene, 2-phenylethanol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, diethyleneglycol, triethyleneglycol,glycerol, dimethyl sulfoxide (DMSO), N-methyl formamide,N-methylpyrrolidone, and mixtures thereof. In yet another embodiment,the surfactant comprises a surfactant having a high surface tension suchas N-methyl pyrrolidone, which surfactant in some embodiments, helpsenhance the conversion yield of at least 1%. Other examples ofsurfactants include acetonitrile, acetone, ethyl acetate, hexane,diethyl ether, methanol, ethanol, acetyl acetone, diethylcarbonate,chloroform, methylene chloride, diethyl ketone, and mixtures thereof.

In one embodiment, the surfactant is a cationic surfactant, e.g., awater-soluble cationic amine selected from the group of cetyl trimethylammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethylammonium amine, nonyl trimethyl ammonium chloride and dodecyl phenolquaternary amine soaps.

In one embodiment, the surfactant is an organic compound containing atleast one nitrogen atom or phosphorous for a catalyst with acarbosulfide phase with enhanced catalytic activities. The amount of theN-containing/P-containing organic additive to be added generally dependson the desired activity of the final catalyst composition.

In another embodiment, the surfactant is an ammonium or phosphonium ofthe formula R₁R₂R₃R₄Q+, wherein Q is nitrogen or phosphorous and whereinat least one of R₁, R₂, R₃, R₄ is aryl or alkyl of 8-36 carbon atoms,e.g., —C₁₀H₂₁, —C₁₆H₃₃ and —C₁₈H₃₇, or combinations thereof, theremainder of R₁, R₂, R₃, R₄ being selected from the group consisting ofhydrogen, alkyl of 1-5 carbon atoms and combinations thereof. Examplescetyltrimethylammonium, cetyltrimethylphosphonium,octadecyltrimethylphosphonium, cetylpyridinium,myristyltrimethylammonium, decyltrimethylammonium,dodecyltrimethylammonium and dimethyldidbdecylammonium. The compoundfrom which the above ammonium or phosphonium ion is derived may be, forexample, the hydroxide, halide, silicate, or mixtures thereof.

In one embodiment, the surfactant is an N-containing organic additiveselected from the group of aromatic amines, cyclic aliphatic amines,polycyclic aliphatic amines, and mixtures thereof. In anotherembodiment, the N-containing organic additive is selected from compoundscontaining at least one primary, secondary, and/or tertiary amine groupsuch as hexamethylenediamine, monoethanolamine, diethanolamine,triethanolamine and N,N-dimethyl-N′-ethylethylenediamine; aminoalcohols, such as, for example, 2(2-amino ethyl amino)ethanol,2(2-aminoethoxy)ethanol, 2-amino-1-butanol, 4-amino-1-butanol,2,2-diethoxyethylamine, 4,4-diethoxybutylamine, 6-amino-1-hexanol,2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 3-amino-1-propanol;and Amino alkoxy-silanes, such as, for example,(3-glycidoxypropyl)trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane and (3-aminopropyl)trimethoxy-silane, andmixtures thereof.

In one embodiment, the stabilizer/surfactant is an organic carboxylicacid surfactant. In one embodiment, the surfactant is citric acid. Inanother embodiment, the surfactant is pentadecenoic acid, decanoic acid,or other similar long chain acids. In yet another embodiment, thesurfactant is alginic acid. In a fourth embodiment, the surfactant ismaleic acid.

Component—Hydrocarbon Transforming Agent: The hydrocarbon transformingagent transforms the catalyst precursor (hydrophilic) to an oil basedactive catalyst (hydrophobic) of the formula(M)_(a)(L)_(b)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h). The nature of thehydrocarbon is not critical, and can generally include any hydrocarboncompound, acyclic or cyclic, saturated or unsaturated, unsubstituted orinertly substituted, and mixtures thereof, and which hydrocarboncompound is liquid at ordinary temperatures.

In one embodiment, the weight ratio of the water base catalyst precursorto the hydrocarbon compound is in the range of 1:10 to 5:1. In a secondembodiment, the weight ratio of the water base catalyst precursor to thehydrocarbon compound is in the range of 1:5 to 1:1. In one embodimentwith the present of a promoter metal Group VIII, the weight ratio of theGroup VIII and Group VIB metal components to the hydrocarbon oil mediumis in the range of 1:1 to 1:500. In another embodiment, in the range of1:2 to 1:150. In a third embodiment, from 1:3 to 1:100. In a fourthembodiment, from 1:5 to 1:50. In a fifth embodiment, from 1:7 to 1:20.

In one example, the hydrocarbon compound is selected from the group ofstraight chain saturated acyclic hydrocarbons as octane, tridecane,eicosane, nonacosane, or the like; straight chain unsaturated acyclichydrocarbons as 2-hexene, 1,4-hexadiene, and the like; branched chainsaturated acyclic hydrocarbons as 3-methylpentane, neopentane,isohexane, 2,7,8-triethyldecane, and the like; branched chainunsaturated acyclic hydrocarbons such as3,4-dipropyl-1,3-hexadiene-5-yne, 5,5-dimethyl-1-hexene, and the like;cyclic hydrocarbons, saturated or unsaturated, such as cyclohexane,1,3-cyclohexadiene, and the like; and including such aromatics ascumene, mesitylene, styrene, toluene, o-xylene, or the like. In yetanother embodiment, the hydrocarbon compound is derived from petroleum,including admixtures of petroleum hydrocarbons characterized as virginnaphthas, cracked naphthas, Fischer-Tropsch naphtha, light cat cycleoil, heavy cat cycle oil, and the like, typically those containing fromabout 5 to about 30 carbon atoms.

In one embodiment, the hydrocarbon compound has a kinetic viscosityranging from 2 cSt to 15 cSt@100° C. In a second embodiment, thehydrocarbon oil has a kinematic viscosity of at least 2 cSt at 100° C.In a third embodiment, from 5 cSt to 8 cSt at 100° C. The hydrocarbonoil causes a transformation of the catalyst precursor from a water basedto an oil based. In one embodiment, the ratio of the Group VIB metal (M)to hydrocarbon is less than 1.0. In a second embodiment, the ratio isless than 0.5. In a third, less than 0.1. In one embodiment with thekinematic viscosity of the hydrocarbon transforming agent being below 2cSt@100° C. or above about 15 cSt@100° C., the transformation of thecatalyst precursor results in catalyst particles agglomerating orotherwise not mixing. In one embodiment, the hydrocarbon compound is avacuum gas oil (VGO).

Other Optional Components: If desired, materials including other metalscan be added in addition to the components described above. Thesematerials include any material that is added during conventionalhydroprocessing catalyst preparation. Suitable examples are phosphoruscompounds, boron compounds, additional transition metals, rare earthmetals or mixtures thereof. Suitable phosphorus compounds includeammonium phosphate, phosphoric acid, or organic phosphorus compounds.Suitable additional transition metals that can be added to the processsteps include are, e.g., rhenium, ruthenium, rhodium, iridium, chromium,vanadium, iron, cobalt, platinum, palladium, and cobalt. In oneembodiment, the additional metals are applied in the form ofwater-insoluble compounds. In another embodiment, the additional metalsare added in the form of water soluble compounds. Apart from addingthese metals during the process, it is also possible to composite thefinal catalyst composition therewith the optional materials. It is,e.g., possible to impregnate the final catalyst composition with animpregnation solution comprising any of these additional materials.

In one embodiment to help reduce coking, the additional optionalcomponent added is phosphorous in the form of phosphomolybdic acidhaving an atomic ratio of P/Mo ranging from about 0.08:1 to 0.01:1.

Method for Making Catalyst: In one embodiment, the preparation methodallows systematic varying of the composition and structure of thecatalyst by controlling the relative amounts of the elements, the typesof the feed components (reagents) including surfactant additives if any,the length and severity of the various reactions.

In the invention, sulfiding (sometimes referred to as “presulfiding”) ofthe metal precursor(s) to form a sulfided catalyst precursor isperformed prior to the introduction of the catalyst into ahydroprocessing reactor (thus ex-situ sulfiding).

In one embodiment, the first step is forming a Group VIB metal componentin solution. In one example, aqueous ammonia is brought into contactwith at least a Group VIB metal compound, such as molybdenum oxide ortungsten oxide, forming a water soluble oxygen-containing compound suchas ammonium molybdate or tungstate.

In one embodiment with the optional use of a least a promoter metal, theGroup VIB metal component in solution is brought into contact with atleast a promoter metal component in solution. The addition of thepromoter metal can lead to precipitate, which does not interfere withsulfiding process as the sulfiding can be done in slurry or fullydissolved form. In one embodiment, the Group VIB metal is sulfided firstbefore it is brought into contact with at least a promoter metalcomponent in solution.

In one embodiment, the mixture is kept at a sufficient high pH tocomplex the promoter metal forming a precipitate. In yet anotherembodiment, the mixing is carried out at a sufficient temperature andpH, at which the promoter metal compound and the Group VIB metalcompound precipitate. In another embodiment, at least one metalcomponent is added in the solid state and at least one metal componentis added in a solute state. In another embodiment and depending on thepromoter metal used, the mixture is kept at a pH of at least 8 toprevent a precipitate from forming.

In one embodiment, the mixing of Group VIB and promoter metal is in thecarried out at 0-300° F. in one embodiment, between 25-200° F. in asecond embodiment, and in the range of 70-180° F. in a third embodiment.If the temperature is below the boiling point of the protic liquid, suchas 212° F. in the case of water, the process is generally carried out atatmospheric pressure. Above this temperature, the reaction is generallycarried out at increased pressure, such as in an autoclave. In oneembodiment, the precipitation reaction is at between 0 to 3000 psig. Ina second embodiment, between 100 to 1000 psig.

In one embodiment, the mixture is kept at its natural pH during thereaction step. The pH is in the range of 0-12 in one embodiment, between2-10 in a second embodiment, and 3-8 in a third embodiment. Changing thepH can be done by adding base or acid to the reaction mixture, or addingcompounds, which decompose upon temperature increase into hydroxide ionsor H⁺ ions that respectively increase or decrease the pH. Examplesinclude urea, nitrites, ammonium hydroxide, etc. In one embodiment, thepH is controlled such that the pH at the beginning of the reactiondiffers from the final pH after precipitation.

In one embodiment, the reaction of the Group VIB metal compound(sulfided or unsulfided) and the promoter metal components is carriedout with water-soluble nickel, molybdenum and tungsten components underconditions described above. The solution may further comprise otherpromoter metal components, e.g., cobalt or iron components such asCo(NO₃)₂, Co(CH₃CO₂)₂, or chromium components. In one embodiment, thereaction of the Group VIB and the optional promoter metal component isin an organic solvent with added water under H₂-containing gas pressure,with the organic solvent being a hydrocarbon mixture of alkanes andaromatic compounds.

In one embodiment, the reaction is carried with the appropriate metalprecursors resulting in precipitate combinations ofnickel/molybdenum/tungsten, cobalt/molybdenum/tungsten ornickel/cobalt/molybdenum/tungsten. These types of precipitates have ahigher surface area than precipitates prepared from the Group VIB metaland the promoter metal, e.g, a group non-noble VIII metal. In oneembodiment with multiple Group VIII precursors being employed, nickeland cobalt make up at least 50 wt. % of the total of Group VIIInon-noble metal components. In another embodiment with multiple GroupVIB precursors being employed, molybdenum and tungsten make up at least50 wt. % of the total of Group VIB metal components.

In one embodiment, the reaction of Group VIB metal and promoter metalcomponents is carried out with water-soluble nickel and molybdenum,wherein nickel is used at a ratio of 0.1-1 atom per Mo atom. In a secondembodiment, at a ratio of 0.5 nickel atom per each Mo atom.

The metal precursors can be added to the reaction mixture in solution,suspension or as such. If soluble salts are added as such, they willdissolve in the reaction mixture and subsequently be precipitated. Inone embodiment, the solution is heated optionally under vacuum to effectprecipitation and evaporation of the water.

In one embodiment, in addition to the metal precursors, at least abinder material can be optionally added to the mixture. Binder materialcan be any of the optional binders described above and/or a precursorthereof. If a precursor binder material is added in the form of thesolution, process condition can be adjusted so that precipitation of thebinder may occur.

In one embodiment, at least a surfactant is added in this step.Surfactant materials to be added including but not limited toN-containing/P-containing organic additives, any of cationic, anionicand nonionic surfactants, as well as other additives includingphosphorus-containing compounds, boron-containing compounds,silicon-containing compounds, fluorine-containing compounds, additionaltransition metal compounds, rare earth metal compounds, or mixturesthereof can be added during precipitation step in a similar way to thatdescribed for the above materials.

In one embodiment, the mixture is subject to activation radiation tofurther improve the catalyst characteristics. In another embodiment, themixture is subject to high intensity ultrasound treatment orelectromagnetic energy to reduce the particle size and thus the catalystcharacteristics.

In one embodiment prior to the sulfidation step, the mixture isoptionally isolated from the liquid using methods known in the art suchas filtration, centrifugation, decantation, or combinations thereof. Inanother embodiment prior to the sulfidation step, the mixture isoptionally treated with a sulfur additive or a commercially availablecatalyst presulfiding agent. In yet another embodiment prior to thesulfidation step, the mixture is optionally treated with at least anN-containing/P-containing organic additive.

In one embodiment, an aqueous solution of a Group VIB metal compound,e.g., ammonium p-tungstate or a molybdate such as ammonium molybdate, isbrought into contact with a sulfiding agent in the sulfidation step. Inanother embodiment with at least a promoter metal L, the mixture formedfrom the reaction of the metal precursors is converted into a sulfidedcatalyst precursor upon contact with the sulfiding agent. In yet anotherembodiment with a promoter metal L, the aqueous solution of a Group VIBmetal compound is first brought into contact with a sulfiding agent toform a sulfided metal precursor, which is subsequently promoted with apromoter metal compound. In yet another embodiment, the Group VIB metalcompound and the promoter metal L are brought into contact with asulfiding agent separately to form sulfided metal precursors, then thesulfided metal precursors are subsequently brought into contact formingthe catalyst precursor.

In one embodiment in addition to the sulfiding agent, at least a sulfuradditive and optionally other additives known in the art, e.g.,phosphorous-containing promoters, etc., can be separately or in amixture with the sulfiding agent to increase the incorporation of sulfurin the catalyst. In one embodiment, instead of or in addition to theaddition of surfactants in other steps, at least a surfactant is addedin the sulfiding step.

In one embodiment, the sulfidation is carried out at a temperatureranging from room temperature to 300° F. and for ½ hr. to 24 hours. Inanother embodiment, the sulfidation is at 50° F. to 250° F. In yetanother embodiment, the sulfidation is between 50-200° F. In a fourthembodiment, the sulfidation is between 60-150° F. In one embodiment, thesulfidation is at between 0 to 3000 psig. In a second embodiment,between 100 to 1000 psig. In a third embodiment, the sulfidationpressure is less than 500 psig.

In yet another embodiment, the sulfidation is carried out at atemperature ranging from 50° F. to 300° F., from 10 minutes to 5 days,and under a H₂-containing gas pressure. If the sulfidation temperatureis below the boiling point of the sulfiding agent, such as 60-70° F. inthe case of ammonium sulfide solution, the process is generally carriedout at atmospheric pressure. Above the boiling temperature of thesulfiding agent/optional components, the reaction is generally carriedout at an increased pressure, such as in an autoclave.

In yet another embodiment, the sulfidation is with an aqueous ammoniumsulfide solution at a temperature between ambient and 250° F., and inthe presence of at least a sulfur additive selected from the group ofthiodazoles, thio acids, thio amides, thiocyanates, thio esters, thiophenols, thiosemicarbazides, thioureas, mercapto alcohols, and mixturesthereof.

In one embodiment with the sulfiding step being carried out in aqueoussolution, the resultant product of the sulfiding step is a slurry in anaqueous solution. Analyses will show that the catalyst precursor productof the sulfiding step is catalytically active, although not in optimumform for use in hydroprocessing operations.

In one embodiment, the process can be extended to include blending metalsulfide powders, e.g., molybdenum sulfide powders, into the catalystprecursor to further enhance the activity of the catalyst.

In one embodiment after sulfiding, the catalyst precursor is optionallyisolated from the liquid using methods known in the art such asfiltration, centrifugation, decantation, or combinations thereof, underan inert atmosphere comprising any of nitrogen, refinery gas, a gashaving little or no oxygen, and mixtures thereof. In the next step, thecatalyst precursor powder is impregnated again with the sulfiding agent,e.g., ammonium sulfide (NH₄)₂S solution, and/or optional sulfuradditives.

In one embodiment after sulfiding, the catalyst precursor is subject toan optional ammonia removal step. Ammonia removal has a favorable effectupon catalyst activity because ammonia is a depressant to the activityof a hydrogenation catalyst. Ammonia removal is beneficial to catalystactivity because any ammonia present can be adsorbed at metal sites andmay constitute a catalyst poison. In one embodiment, the sulfided waterbased slurry from the sulfiding step is subject to a simple aqueousphase ammonia flashing step by cooling and depressurizing the slurrystream. Ammonia can be flashed off together with any generated hydrogensulfide and hydrogen present in the system.

The hydrogen containing gas in the above steps of the process can besubstantially pure hydrogen, or can be mixtures of hydrogen with othergases such as nitrogen, helium, methane, ethane, carbon monoxide orhydrogen sulfide.

In one embodiment with the use of molybdenum as the Group VIB metal andnickel as the Group VIII promoter, the sulfiding is controlled for aS/Group VIB ratio of about 3 (i.e., MoS_(x) wherein x=3), wherein thecrystalline of Group VIB system is destroyed to form a finely dispersed,amorphous molybdenum sulfide catalyst precursor. In one embodiment, thesurface area of the catalyst precursor at this stage is less than 3m²/g. In the activation step at increasing temperature and/or reducingpH and in the presence of the sulfiding agent, e.g., hydrogen gascontaining H₂S, it is believed that the value of x in catalyst precursorMoS_(x) is now 2, which is highly active for hydrogenation and oxidationreactions, and characterized by a high surface area of greater than 50m²/g and highly pyrophoric.

Forming Oil-Based Bulk Catalyst Composition: In this step, the catalystprecursor is mixed with a hydrocarbon compound and is transformed intoan oil based catalyst of the formula(M^(t))_(a)(L_(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h).In one embodiment, it is believed that in the transformation process,the hydrophilic sulfide catalyst precursor is transformed into an activehydrophobic sulfide species in the form of fine dispersion of smallaggregates.

In one embodiment, instead of or in addition to the addition ofsurfactants in other steps, at least a surfactant is added to thecatalyst precursor and hydrocarbon compound in this transformationphase.

In one embodiment, the mixing is continuous in a high shear mode, e.g.,from 100 to 1600 RPM, and from about 10 minutes to 24 hours, forming ahomogeneous slurry. The mixing can be done within a continuous stirredtank, or it can be done by other means including an in-line static mixer(e.g., with a plurality of internal baffles or other elements), adynamic high-shear mixer (vessel with propeller for very high turbulent,high shear mixing), or a combination of the above for turbulent mixingcondition. As used herein, turbulent mixing conditions means sufficientmixing for a flow with a Reynolds number of at least 2000. In a secondembodiment, turbulent mixing means sufficient mixing for a Reynoldsnumber of at least 3000. In a third embodiment, a Reynolds numberranging from 3200 to 7200.

In one embodiment, the reaction time in this step ranges from 30 minutesto 3 hours. In another embodiment, the reaction time ranges from 1 to 2hrs.

In one embodiment, the process conditions in the transformation step aresufficient to form the final catalyst, in terms that at least a portionof the water is in the liquid. In one embodiment, “a portion of thewater” means that at least 50% of the water in the mixture is maintainedin a liquid phase. In a second embodiment, “a portion of the water”means that less than 90% of the water in the mixture is maintained inthe liquid phase. In a third embodiment, less than 70% of the water inthe mixture is maintained in the liquid phase. In a fourth embodiment,less than 50% of the water in the mixture is maintained in the liquidphase.

In one embodiment, the temperature of the transformation step ismaintained at a temperature of 50-600° F. In a second embodiment, thetemperature is maintained at a temperature of 100-500° F. In a thirdembodiment, the transformation temperature ranges from 150-450° F. In afourth embodiment, the transformation temperature ranges from 200 to475° C.

In one embodiment, the pressure of the transformation step is maintainedin the range of 0-1000 psig. In a second embodiment, it is between200-500 psig. In a third embodiment, from 300-450 psig.

In one embodiment with the use of a light oil such as naphtha (with aboiling point above the boiling point of water) as the hydrocarbontransforming agent, in order to keep the oil at liquid at a hightemperature, e.g., a temperature above 200° C. (392° F.), thetransformation step is carried out at a pressure in the range of about15 MPa (2,175 psi) to about 20 MPa (2,900 psi). With the use of naphtha,after the transformation step, the light oil can be convenientlyvaporized in order to obtain the concentrated slurry catalyst. Thevaporized oil can be recycled for subsequent reuse in the catalysttransformation step or elsewhere in the hydroprocessing system. In oneembodiment, the removal of the light naphtha is done by distillation. Inanother embodiment, by decantation or phase separation. Additionally,with the use of a light oil as a transforming agent, there is lessagglomeration and the concentrated slurry catalyst can be subsequentlyquickly dispersed into heavy oil feed in a hydroconversion process.

In one embodiment, the mixing is under an inert atmosphere comprisingany of nitrogen, refinery gas, a gas having little or no oxygen, andmixtures thereof. In another embodiment, the mixing is under aH₂-containing gas pressure. In a third embodiment, hydrogen gas is addedat a relatively low rate before and after the reactor in which thehydrocarbon/catalyst precursor mixing takes place. In one embodiment,the H₂ flow to the transformation step is kept at 100 to 2000 SCFB(“Standard Cubic Feet per Barrel” of hydrocarbon compound feed to thereactor). In a second embodiment, the H₂ flow ranges from 300 to 1000SCFB. In a third embodiment, the H₂ flow ranges from 200 to 500 SCFB.

Ammonia removal from the oil based catalyst slurry can be carried outafter the transformation step in one embodiment. The catalyst stream inone embodiment is heated prior to depressurization and ammoniavaporization.

The resultant slurry mixture can go directly to a hydroprocessingreactor without the need for water removal, but the presence of waterwill take up unnecessary room in a hydroprocessing reactor. In oneembodiment, the oil based catalyst slurry mixture is passed to highpressure separator to remove water from the slurry catalyst prior toentering a hydroprocessing reactor.

Hydrogen may be added following reactor or directly into the highpressure separator to flash off water and residual H₂S in the catalystslurry. The addition of hydrogen helps change water from liquid to vaporphase, permitting separation from oil slurry in a high pressureseparator. In one embodiment, it is desirable to remove water because itmight interfere with the reactivity of the catalyst. In one embodiment,the amount of water remaining in the slurry catalyst is less than 10 wt.%. In a second embodiment, less than 5 wt. %. In a third embodiment,between 1 to 3 wt. %.

The process steps described herein are in no way limited to the use ofany particular apparatus. Any of the reactors for use in the process canbe batch, semi-batch, or continuously stirred tank reactors (CSTRs), andcan be a vessel equipped heating means having a mechanical stirrer, or astatic mixer, or by means of a recirculating pump. The process steps canbe operated in any of continuous, batch mode, or combinations there offor some of the steps, using a single-stage reactor or multiple-stagereactors. The components (feed streams) can be introducedsimultaneously, or sequentially in any order to the reactor. The term“feed stream” refers to both continuous and batch processed.

FIG. 1 illustrates the steps involved in one embodiment of the process.In a reactor (mixing tank) 10, at least a group VIB metal precursor suchas ammonium heptamolybdate in aqueous solution (feed stream 1) is mixedwith at least a promoter metal precursor such as nickel sulfate inaqueous solution (feed stream 2), forming an intermediate mixture. Inone embodiment, the reaction time in the mixing tank 10 ranges fromabout 1 hour to 10 hours. The temperature in one embodiment ismaintained at 30° C. to 100° C. at a pressure ranging from 100 to 3000psig. In one embodiment, the weight ratio of nickel (or cobalt) tomolybdenum in the group VIII/group VIB precursor feed streams rangesfrom about 1:100 to about 1:2. In a second embodiment, thenickel/molybdenum weight ratio ranges from about 1:25 to 1:10.

In one embodiment (not shown), instead of feeding ammoniumheptamolybdate in aqueous solution to the reactor 10, metal oxidedissolved in aqueous ammonia solution is used as a feed to the process.In this embodiment, there is an additional mixing zone (not shown)wherein a group VIB metal oxide is dissolved in water containing ammoniaat a temperature ranging from 30° C. to 100° C., and at a pressure fromatmospheric pressure to about 100 psig. The dissolved metal oxide (e.g.,MoO₃) in aqueous ammonia is converted to a group VIB metal precursorfeed according to the following reaction:

7 MoO₃ (insoluble crystalline)+6 NH₃+3H₂O->(NH₄)₆Mo₇O₂₄ (soluble).

The catalyst precursor from reactor 10 is moved in line 3 to the nextreactor/mixing tank 20, wherein the catalyst precursor is sulfided witha sulfiding agent, e.g., ammonium sulfide (NH₄)₂S for a period of time 5minutes to 2 hours. In one embodiment, the sulfidation is carried out ata temperature ranging from room temperature to 70° C., and at 0 psig.Optional components (not shown), e.g., N-containing and/or P-containingorganic additive, sulfur additives, etc., can be added to reactor 20 toincrease the incorporation of sulfur in the catalyst precursor formed inthis step.

The water is kept in liquid phase in reactor 20. In one embodiment (notshown), water is changed to vapor phase after reactor 20 in order toflash off the water.

In the next transformation step, the sulfided catalyst precursor fromreactor 20 is moved in line 5 to reactor 30, wherein the catalystprecursor slurry is mixed with hydrocarbon oil feed 6, forming anembodiment of the bulk catalyst. Hydrogen is continuously added to themixture reaction zone, ranging from 300 SCFB (“Standard Cubic Feet perBarrel,” meaning per barrel of hydrocarbon feed) to about 2000 SCFB. Thepressure of the reaction zone generally ranges from about 100 psig toabout 3000 psig. Temperature of the reactor generally ranges from 150 to300° C. Reactor 30 is a CSTR with high shear mixing of greater 500 RPM(“Revolutions Per Minute”) to maintain homogenous slurry in the reactor.The hydrocarbon feed 6 in one embodiment has a kinetic viscosity of 4-10cSt@100° C. The resultant slurry mixture is one embodiment of the activecatalyst composition in admixture with the hydrocarbon oil and havingthe formula

(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h).

In one embodiment, the active catalyst composition is moved in line 7 toa storage tank (not shown), wherein the catalyst slurry is continuouslymixed in storage tank to maintain a homogenous slurry in a hydrogenatmosphere with little or no oxygen. In this way, the catalyst activityand stability are maintained.

The catalyst composition is useful for upgrading carbonaceous feedstockswhich include atmospheric gas oils, vacuum gas oils (VGO), deasphaltedoils, olefins, oils derived from tar sands or bitumen, oils derived fromcoal, heavy crude oils, synthetic oils from Fischer-Tropsch processes,and oils derived from recycled oil wastes and polymers. The catalystcomposition is useful for but not limited to hydrogenation upgradingprocesses such as thermal hydrocracking, hydrotreating,hydrodesulfurization, hydrodenitrification, and hydrodemetallization.

In one embodiment, the bulk catalyst composition is used in a heavy oilupgrading process. As shown in FIG. 1, the catalyst is moved in line 7to a hydrocracking reactor or ebullated bed catalytic reactor 40,wherein the active catalyst slurry is in contact with a heavy oil 8(with optional additives such as modifiers, stabilizers, etc.) and ahydrogen-containing gas (not shown) for sufficient time and atappropriate temperature under hydrocracking conditions. Theconcentration of the active slurry catalyst in the heavy oil feed 8 inone embodiment ranges from about 100 to 20,000 ppm, expressed as weightof metal (molybdenum) to weight of heavy oil feedstock. In oneembodiment for a higher conversion for sulfur, nitrogen and metalremoval, as well as the higher cracking conversion, a higher catalyst tooil ratio is used. In one embodiment with the use of the catalystcomposition, over 95% demetalation conversion and 1000° F. crackingconversion of the heavy oil can be achieved at appropriate processconditions, with a coke yield of less than 1%.

Stream 9 contains combined gas and liquid products (light oil andunconverted heavy oil) as well as catalyst. The resultant light oil isseparated from the solid bulk catalyst and unconverted heavy oil in ahigh pressure separator (not shown). The light oil is sent to a fixedbed reactor typically used for hydrotreating of oil (not shown) tofurther remove sulfur and nitrogen, and to improve product qualities.

It should be noted that the process can be carried out in either a batchand/or continuous mode. In the operation, high shear mixing is desirableto prevent the aqueous slurry from settling or forming thick gel.

In one embodiment, the process is carried out as a batch process with asingle reactor being used for the steps, e.g., forming a mixture,sulfiding, and forming an oil-soluble catalyst in the same equipment,with the steps being carried out in sequence after the completion of theprevious step. In another embodiment, some of the steps are done inbatch mode, and some of the steps are done in the continuous mode. Inone embodiment, sulfiding is done in a continuous mode.

In another embodiment, the process is a batch process with multiplereactors in series and with each step being carried out in a separateCSTR. In a third embodiment, the process is continuous with theprecipitate or catalyst precursor effluents from one step being moved tothe next step in the process. FIG. 2 illustrates an embodiment of aprocess to prepare and activate the bulk catalyst in a continuous.Reactor 10 (at about 100 to 200° F., and 200 to 600 psig) is for theformation of an aqueous solution of a Group VIB metal compound, e.g.,ammonium molybdate. In reactor 20, the Group VIB metal precursor issulfided (at about 100 to 200° F., and 200 to 600 psig). In reactor 30(at about 100 to 200° F., and 200 to 600 psig), the sulfided Group VIBprecursor is promoted with a nickel compound. Reactor 40 is for thetransformation of the catalyst precursor into an oil-based bulk catalyst(at about 300 to 500° F., and 300 to 600 psig). In tank 50 (at about 400to 600° F., and 300 to 600 psig), high shear mixing is employed in orderto maintain the oil-based catalyst as a homogenous slurry. The catalystslurry can be further processed to form a concentrated catalyst slurry.

FIG. 3 illustrates another embodiment of the process for making the bulkcatalyst, with at least a surfactant can be added to any step of theprocess in FIG. 1 to control the morphology and dispersion of the bulkcatalyst. In the figure, feed streams 11, 21, 31, and 41 containing atleast a surfactant can be added to any of the steps in the process.

FIG. 4 illustrates the steps involved in yet another embodiment of theprocess, wherein at least at least a sulfur additive is added to thesulfidation step. As shown in the figure, sulfur additives (stream 22)and optionally, at least a surfactant (stream 21) including but notlimited to N-containing and/or P-containing organic additive, sulfuradditives, etc., can be added to reactor 20 to increase theincorporation of sulfur in the catalyst precursor formed in this step.The sulfur additives 22 can be added separately, or mixed with thesulfiding agent 4, e.g., ammonium sulfide.

Characterization of the Catalyst: Characterization of the catalyst ofthe formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h)having improved morphology and dispersion characteristics can beperformed using techniques known in the art, including elementalanalysis, Surface Area analysis (BET), Particle Size analysis (PSA),Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM),Energy Dispersive X-ray Analysis (EDS), and other methods. In onemethod, electron microscopy is used to complement the x-ray diffractionstudy. In another method, the surface area of the catalyst is determinedusing the BET method. In yet another method, scanning tunnelingmicroscopy (STM) and density functional theory (DFT) can be used tocharacterize the catalyst. Elemental analysis of the catalyst will showpresence of Molybdenum, Nickel, Sulfur, as well as Oxygen, Carbon,Hydrogen, and Nitrogen.

Characteristics of the Catalyst: In one embodiment, the catalyst has apore volume of 0.05-5 ml/g as determined by nitrogen adsorption. In asecond embodiment, the pore volume is 0.1-4 ml/g. In a third embodiment,from 0.1-3 ml/g. In a fourth embodiment, from 0.1-2 ml/g.

In one embodiment, the catalyst has a surface area of at least 5 m²/g.In a second embodiment, a surface area of at least 10 m²/g. In a thirdembodiment, a surface area of at least 50 m²/g. In a fourth embodiment,the surface area is greater than 100 m²/g as determined via the B.E.T.method. In a fifth embodiment, the catalyst has a surface area ofgreater than 200 m²/g. In a sixth embodiment, the catalyst ischaracterized by aggregates of crystallites of 10 to 20 angstrom, for anoverall surface area greater than 100 m²/g.

In one embodiment, the catalyst has an effective suspended medianparticle size of 0.0005 to 1000 microns. In a second embodiment, thecatalyst has a median particle size of 0.001 to 500 microns. In a thirdembodiment, a particle size of 0.005 to 100 microns. In a fourthembodiment, a particle size of 0.05 to 50 microns. In a fifthembodiment, the catalyst in the form of a dispersed suspension ischaracterized by a median particle size of 30 nm to 6000 nm. In a sixthembodiment, the catalyst has an average particle size in the range of0.3 to 20 μm.

In one embodiment, the slurry catalyst has an average particle sizeranging from colloidal (nanometer size) to about 1-2 microns. In anotherembodiment, the catalyst comprises catalyst molecules and/or extremelysmall particles that are colloidal in size (i.e., less than 100 nm, lessthan about 10 nm, less than about 5 nm, and less than about 1 nm), whichin a hydrocarbon diluent, forming a slurry catalyst having “clusters” ofthe colloidal particles, with the clusters having an average particlesize in the range of 1-20 microns with a surface area of greater than100 m²/g. In yet another embodiment, the catalyst composition comprisessingle layer clusters of nanometer sizes, e.g., 5-10 nm on edge.

In one embodiment, the slurry catalyst is characterized by a crystallitesize in the range of 10 to 20 angstrom with a surface area of greaterthan 100 m²/g . In another embodiment, the catalyst is characterized bya macro-structure aggregate with extremely high apparent pore volumesproviding access to the heavy oil molecules to the catalyst. In oneembodiment, it is believed that the crystallite growth is achieved withthe rapid injection of the promoter Group VIII metal compound.

In one embodiment, the catalyst of the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h)is characterized via X-ray powder diffraction (LRD or PXRD) as a poorlycrystalline compound having broad diffraction peaks of low intensity. Asused herein, a broad peak means a peak having a width at ½ height ofmore than 1 degree (in 2-θ scale).

In one embodiment, the catalyst is characterized as having at least onebroad diffusion peak of >1° (in 2θ scale) at ½ height, at any of Braggangles (2θ) 8 to 18°, 32 to 40° and 55 to 65° (from 0 to 70° 2θ scale).In another embodiment, the XRD pattern of the catalyst shows at leastone broad peak having width at ½ height of >2 degrees (in 2θ scale),with the broad peak being at any of Bragg angles 8-18°, 32-40° and55-65° in the 2θ scale. In yet another embodiment, XRD pattern of thecatalyst shows that at least one broad peak of >=5 degrees wide at ½height, with the broad peak being at any one of Bragg angles 8-18°,32-40° and 55-65° in the 2θ scale.

FIG. 5 shows the powder X-ray diffraction pattern of the intermediatecatalyst precursor sample from one embodiment (solids filtered from thewater-based pre-catalyst slurry of Example 1), with a broad peakappearing between 7-17 degrees and also between 33-43 degrees (in 2θscale) and also as indicated by circles on the figure. For comparison, aPXRD spectrum of stock crystalline ammonium tetrathiomolybdate is shownin FIG. 6 with narrow and well-defined peaks being observed at 14-15 and28 degrees (in 2θ scale).

FIG. 7 shows the powder X-ray diffraction pattern of a catalyst samplein one embodiment prepared along the line of Example 10. X-raydiffraction analyses show that the catalyst exhibits poor crystallinitywith diffuse/broad Bragg peaks (width of peaks at ½ height is >1° in2-theta scale) at 8-15°, 32-40° and 55-65°. For comparison, FIG. 8 showsa PXRD spectrum of crystalline MoS₂ with well-defined diffraction peaksof high intensity. Catalytic activity of this material is much lowerthan that of a catalyst in an embodiment of the invention.

FIG. 9 shows a volume-based PSA spectrum of extracted catalyst solids inone embodiment of the invention. Most of the particles fall into the 0.3to 20 μm average particle size range, with peak distribution frequenciesat 1 cm and 10 cm, suggesting a bi-modal type distribution.

Use of The Catalyst: The catalyst composition can be used in virtuallyall hydroprocessing processes to treat a plurality of feeds underwide-ranging reaction conditions such as temperatures of from 200 to450° C., hydrogen pressures of from 5 to 300 bar (72 to 4351 psi or 0.5to 30 MPa), liquid hourly space velocities of from 0.05 to 10 h⁻¹ andhydrogen treat gas rates of from 35.6 to 2670 m³/m³ (200 to 15000SCF/B).

In one embodiment, the process pressure ranges from about 10 MPa (1,450psi) to about 25 MPa (3,625 psi), about 15 MPa (2,175 psi) to about 20MPa (2,900 psi), less than 22 MPa (3,190 psi), or more than 14 MPa(2,030 psi). The liquid hourly space velocity (LHSV) of the feed willgenerally range from about 0.05 h⁻¹ to about 30 h⁻¹, about 0.5 h⁻¹ toabout 25 h⁻¹, about 1 h⁻¹ to about 20 h⁻¹, about 1.5 h⁻¹ to about 15h⁻¹, or about 2 h⁻¹ to about 10 h⁻¹. In some embodiments, LHSV is atleast 5 h⁻¹, at least 11 h⁻¹, at least 15 h⁻¹, or at least 20 h⁻¹. Inanother embodiment, the LHSV ranges from 0.25 to 0.9 h⁻¹. In yet anotherembodiment, the LHSV ranges from 0.1 to 3 LHSV. The (contacting zone)process temperature ranges from about 410° C. (770° F.) to about 600° C.(1112° F.) in one embodiment, less than about 462° C. (900° F.) inanother embodiment, more than about 425° C. (797° F.) in anotherembodiment.

The hydroprocessing can be practiced in one or more reaction zones andcan be practiced in either countercurrent flow or cocurrent flow mode.By countercurrent flow mode is meant a process wherein the feedstreamflows countercurrent to the flow of hydrogen-containing treat gas. Thehydroprocessing also includes slurry and ebullated bed hydrotreatingprocesses for the removal of sulfur and nitrogen compounds and thehydrogenation of aromatic molecules present in light fossil fuels suchas petroleum mid-distillates, e.g., hydrotreating a heavy oil employinga circulating slurry catalyst.

The feeds for use in hydroprocessing processes using the catalyst mayinclude petroleum and chemical feedstocks such as olefins, reducedcrudes, hydrocrackates, raffinates, hydrotreated oils, atmospheric andvacuum gas oils, coker gas oils, atmospheric and vacuum resids,deasphalted oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes andmixtures thereof. Specific examples range from the relatively lightdistillate fractions up to high boiling stocks such as whole crudepetroleum, reduced crudes, vacuum tower residua, propane deasphaltedresidua, brightstock, cycle oils, FCC tower bottoms, gas oils includingcoker gas oils and vacuum gas oils, deasphalted residua and other heavyoils. In one embodiment, the feedstock is a C₁₀₊ feedstock. In anotherthe feedstock is selected from distillate stocks, such as gas oils,kerosenes, jet fuels, lubricating oil stocks boiling above 230° C.,heating oils, hydrotreated oil stock, furfural-extracted lubricating oilstock and other distillate fractions whose pour point and viscosityproperties need to be maintained within certain specification limits.

In one embodiment, the feedstocks contain a substantial amount ofnitrogen, e.g. at least 10 wppm nitrogen, in the form of organicnitrogen compounds. The feeds can also have a significant sulfurcontent, ranging from about 0.1 wt. % to 3 wt. %, or higher. In yetanother embodiment, the feedstock is a feed derived from crude oils,shale oils and tar sands as well as synthetic feeds such as thosederived from the Fischer-Tropsch process, having initial boiling pointsof greater than 315° C. or higher. Specific examples include reducedcrudes, hydrocrackates, raffinates, hydrotreated oils, atmospheric gasoils, vacuum gas oils, coker gas oils, atmospheric and vacuum resids,deasphalted oils, slack waxes and Fischer-Tropsch wax, and mixturesthereof. In one embodiment, the feedstock is a mixture of gas oil from acoker and vacuum distillation from conventional crudes, derived fromdistillation towers (atmospheric and vacuum), hydrocrackers,hydrotreaters and solvent extraction units, and may have wax contents ofup to 50% or more. In yet another embodiment, the feed stock is selectedfrom mid-distillates from fossil fuels such as light catalytic cyclecracking oils (LCCO); distillates derived from petroleum, coal, bitumen,tar sands, or shale oil; heavy catalytic cracking cycle oils (HCCO),coker gas oils, oils derived from recycled oil wastes and polymers,vacuum gas oils (VGO) and heavier resids, which contain several percent3+ ring aromatics, particularly large asphaltenic molecules.

The hydrotreating processes using the catalyst may be suitable formaking lubricating oil basestocks meeting Group II or Group III base oilrequirements. In one embodiment, the catalyst is for use in ahydroprocessing process producing white oils. White mineral oils, calledwhite oils, are colorless, transparent, oily liquids obtained by therefining of crude petroleum feedstocks.

The catalyst can be applied in any reactor type. In one embodiment, thecatalyst is applied to a fixed bed reactor. In another embodiment, twoor more reactors containing the catalyst may be used in series.

In one embodiment, the catalyst is added to the feedstock (catalyst tooil ratio) at a rate of 0.01 to 3 wt. %. In a second embodiment, at arate of 0.25 to 2 wt. %. In a third embodiment, at a rate of 100 to 2000ppm active metals, i.e., the group VIB metals “M” in the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h).In a fourth embodiment, the catalyst is added to the feedstock at asufficient rate for the total amount of Mo in the reaction zone reaches0.005 to 0.05 wt. % (based on the total weight of the feedstock).

In one embodiment of a hydrogenation process employing the catalyst ofthe formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),the heavy hydrocarbon is hydrogenated to a value of up to 90% by mass.

The catalyst of the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),even without the presence of promoter metal L in some embodiments (b=0),is characterized as giving excellent conversion rates in the upgrades ofheavy oil, i.e., giving conversion rates of at least 90% in oneembodiment, at least 92.5% in a second embodiment, and at least 95% in athird embodiment. In one embodiment of a heavy oil upgrade systememploying the catalyst of the formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),at least 98 wt. % of heavy oil feed is converted to lighter products. Ina second embodiment, at least 98.5% of heavy oil feed is converted tolighter products. In a third embodiment, the conversion rate is at least99%. In a fourth embodiment, the conversion rate is at least 95%. In afifth embodiment, the conversion rate is at least 80%. As used herein,conversion rate refers to the conversion of heavy oil feedstock to lessthan 1000° F. (538° C.) boiling point materials.

EXAMPLES

The following illustrative examples are intended to be non-limiting.Unless specified otherwise, the catalytic activity of the catalystsprepared in the examples are tested for Hydrodenitrogenation (HDN),Hydrodesulfurization (HDS), as well as API gravity change andMicrocrystalline Carbon Residue (MCRT). The results are presented inTable 2.

Example 1 Base Example

33.12 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) wasdissolved in 100 g of water in a glass vessel fitted with an overheadmechanical stirrer, and 14.1 g of concentrated ammonia solution (28 wt.% NH₄OH in H₂O) was added. A solution of 8.1 g of nickel sulfatehexahydrate (NiSO₄·6H₂O) in 32 g of water was added to the firstsolution, all at ambient temperature, producing an emerald-greensuspension. This suspension was heated to 70° C. under atmosphericpressure, and 101 g of ammonium sulfide ((NH₄)₂S) solution in water(40-44 wt. %) was added slowly, over the course of 45 minutes. Afterthat, the mixture was heated with stirring for an additional 60 minutes.The volume of the reaction mixture was reduced in half on a rotaryevaporator. The resulting water-based catalyst precursor was transformedto a final oil-based catalyst with medium cycle oil (MCO) and hydrogenin a pressure test autoclave in situ.

Example 2 Lower Ammonia Concentration

The procedure is similar to Example 1, using 33.12 g of ammoniumheptamolybdate tetrahydrate to dissolve in 100 g of water in a glassvessel fitted with an overhead mechanical stirrer, and in this case 5 gof concentrated ammonia solution was added. A solution of 8.1 g ofnickel sulfate hexahydrate in 32 g water was added to the firstsolution, all at ambient temperature, producing a light-greensuspension. This suspension was heated to 70° C. under atmosphericpressure, and 101 g of ammonium sulfide solution was added slowly, overthe course of 45 minutes. After that, the mixture was heated withstirring for an additional 60 minutes. The rest of the procedures andtests were similar to Example 1.

Example 3 Higher Ammonia Concentration

8.1 g of nickel sulfate hexahydrate was dissolved at ambient temperaturein a mixture of 100 g of water and 15.3 g of concentrated ammoniasolution in a glass vessel fitted with an overhead mechanical stirrer.Then, 33.12 g of ammonium heptamolybdate tetrahydrate was added to thismixture, forming a green suspension. Additional 11.4 g of ammoniasolution was added, to yield a clear deep-blue solution. This solutionwas heated to 70° C. under atmospheric pressure, and 101 g of ammoniumsulfide solution in was added slowly, over the course of 45 minutes.After that, the mixture was heated with stirring for an additional 60minutes. The rest of the procedures and tests were similar to Example 1.

Example 4 Very Low Ammonia Concentration Solid AHM Added

8.1 g of nickel sulfate hexahydrate was dissolved at ambient temperaturein a mixture of 100 mL of water and 0.2 g of concentrated ammoniasolution in a glass vessel fitted with an overhead mechanical stirrer.Then, 33.12 g of ammonium heptamolybdate tetrahydrate (AHM) was added tothis mixture, forming a heavy light-green suspension. This solution washeated to 70° C. under atmospheric pressure, and 101 g of ammoniumsulfide solution was added slowly, over the course of 45 minutes. Afterthat, the mixture was heated with stirring for an additional 60 minutes.The rest of the procedures and tests were similar to Example 1.

Example 5 Slow Addition of Sulfiding Reagent

The procedure is similar to Example 2, using 33.12 g of ammoniumheptamolybdate tetrahydrate to dissolve in 100 g of water with 5 g ofconcentrated ammonia solution, in a glass vessel fitted with an overheadmechanical stirrer. A solution of 8.1 g of nickel sulfate hexahydrate in32 g water was added to the first solution, all at ambient temperature,producing a light-green suspension. This suspension was heated to 70° C.under atmospheric pressure, and 101 g of ammonium sulfide solution wasadded slowly, over the course of 120 minutes. After that, the reactionwas stopped, and the rest of the procedures and tests were similar toExample 1.

Example 6 Rapid Addition of Sulfiding Reagent, with Continued Heating

The procedure is similar to Example 5, except that the addition of 101 gof ammonium sulfide solution was done over 3 minutes. After that, thereaction was heated with stirring for an additional 120 minutes, and therest of the procedures and tests were similar to Example 1.

Example 7 Rapid Addition of Sulfiding Reagent

The procedure is similar to Example 1, except that the addition of 101 gof ammonium sulfide solution was done over 10 minutes, and the reactionwas stopped immediately after that. The rest of the procedures and testswere similar to Example 1.

Example 8 Higher Amount of Nickel Relative to Molybdenum—Mo:Ni=5:1

The procedure is similar to Example 2, using 33.12 g of ammoniumheptamolybdate tetrahydrate to dissolve in 100 g of water mixed with 5 gof concentrated ammonia solution, in a glass vessel fitted with anoverhead mechanical stirrer. A solution of 16.2 g of nickel sulfatehexahydrate in 32 g water was added to the first solution, all atambient temperature, producing a green suspension. This suspension washeated to 70° C. under atmospheric pressure, and 100 g of ammoniumsulfide solution (44 wt. %) was added slowly, over the course of 45minutes. After that, the mixture was heated with stirring for anadditional 60 minutes. The rest of the procedures and tests were similarto Example 1.

Example 9 Higher Amount of Nickel Relative to Molybdenum—Mo:Ni=3:1

The procedure was similar to Example 2, however 26.9 g of nickel sulfatehexahydrate solution in 39 g water, was used, producing a green-yellowsuspension in the first step. Further procedures and tests were similarto Example 1.

Example 10 Large-Scale Synthesis of Oil Transformed Catalyst

2663 g of ammonium dimolybdate was combined with 1850 g of hot deionized(DI) water, and 1566 g of ammonium hydroxide solution (28% in water).The mixture was stirred and the reactor heated to ˜140° F. Afterstirring for 20 minutes, a slurry of 673 g of nickel sulfate hexahydratein 667 g of ammonium hydroxide (28% in water) was added. The mixture wasstirred for four hours to dissolve any solids present. At this time thereaction mixture was a dark blue solution. An aqueous ammonium sulfidesolution (41.9%) was added via a peristaltic tube pump with an additionspeed of 91 g·min-1. A total of 9061 g of ammonium sulfide solution wasadded over 100 minutes.

The bulk of the water-based catalyst precursor was subjected to batchtransformation, by mixing 3796 g of aqueous based precursor and 3000 gof vacuum gas oil (VGO) in a 3-gallon autoclave and heating to 400° F.under 400 psi of nitrogen. Then hydrogen was added with 32 SCF/h and thereduction was carried out until no H₂S was detected in the exit gasstream. This gave the final catalyst slurry was tested with medium cycleoil (MCO) and hydrogen in a pressure test autoclave for HDN/HDS/API/MCRTactivity.

Example 11 Reduced Amount of Water, Hydrazine Additive

8.22 g of nickel sulfate hexahydrate were dissolved in 20 g of DI water,followed by the addition of 8.05 g of 28% ammonium hydroxide solution. Adark blue clear solution formed, pH=9.6 at 25° C. In a separatecontainer 18 g of 28% ammonium hydroxide solution was mixed with 12 g ofDI water. 33.13 g of ammonium heptamolybdate tetrahydrate (AHM) wasadded to the above solution with stirring. The resulting mixture washeated in a water bath at 40° C. for 15 min followed by the addition ofnickel sulfate solution. The pH was adjusted to 8.5 with 2 ml ofconcentrated ammonium hydroxide solution. As the result a clear solutionwas obtained. The solution was heated to 80° C. under ambient pressure.94.48 g of ammonium sulfate solution (˜50% wt.) was added slowly, overthe course of 1 hr. The mixture was kept for additional 30 min at 80° C.followed by addition of 30 ml of hydrazine. The mixture was stirred for2 hrs and then cooled down to room temperature. The final pH was 9.1.The rest of the procedures and tests were similar to Example 1, exceptthe final product was sonicated for 5 min.

Example 12 Cobalt/Molybdenum Catalyst

6.03 g of 28% ammonium hydroxide solution was added to 44.01 g of DIwater. The solution was heated to 60° C. 33.12 g of ammoniumheptamolybdate tetrahydrate was added to the above solution and stirredtill clear. The resulting solution was heated to 70° C., pH=6.6 at 60 C,and 92.03 g of concentrated ammonium sulfide (50 wt %) solution wasadded slowly over the course of 45 min followed by the addition of 7.8 gof cobalt acetate tetrahydrate. The mixture was stirred for another 2hrs. at 75° C. and then cooled to room temperature. The rest of theprocedures and tests were similar to Example 1.

Example 13 Nickel/Molybdenum/Tungsten Catalyst, 6 wt. % Mo/13 wt. % W/8wt. % Ni

17.65 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) wasdissolved in 800 g of water in a glass vessel fitted with an overheadmechanical stirrer. 24.66 g of ammonium metatungstate hydrate was addedto the above solution, pH=5.3 at 22° C. The pH was adjusted to 9.7 with30 ml of 28 wt % ammonium hydroxide and the solution was heated to 90°C. 58.21 g of nickel sulfate hexahydrate (NiSO₄·6H₂O) was dissolved in50 g of DI water, heated to 90° C., and added to the first solution. Aresulting suspension was stirred at the temperature for 60 min. and thenfiltered hot to produce an apple green filter cake. The cake was washedwith DI water and 109 g of it were mixed with 103 g of DI water,sonicated for 20 min., and heated to 70° C. under atmospheric pressurefollowed by addition of 100 g of ammonium sulfide ((NH₄)₂S) solution inwater (50 wt. %) over the course of 60 minutes. After that, the mixturewas heated with stirring for an additional 60 minutes. The rest of theprocedures and tests were similar to Example 1.

Example 14 Catalyst Screening Studies

For the screening studies, the feed consists of highly aromatic FCC(“fluidized catalyst cracking”) cycle oil which has the aromaticcomplexity of heavy oil but without the difficult-to-analyze asphalt.The operating conditions are as follows: 725° F. for reactiontemperature, an equivalent of 3000 SCFB hydrogen to oil ratio, 1250 psighydrogen partial pressure, 4 hours residence time, and catalyst to oilratio equal to 1.8 percent by weight of feed.

These conditions, although consistent with those usually employed incycle oil hydrogenation units are substantially more demanding becauseof the very low catalyst to oil ratio used in this study. summarizesboth the operating conditions used as well as the quality of thescreening feed. Table 2 presents the results of the experiments.

TABLE 1 Catalyst Screening Conditions and Feed Inspections CatalystScreening Conditions: Catalyst to Oil Ratio, wt/wt, % 1.8 TemperatureProtocol: Ramp to CAT, Hrs (F./Min.) 2.5 (5.0) CAT, F. 725 Soak at CAT,Hrs 4.0 Quench, Time, 1.0 Minutes for 450 F. CAT Initial Pressure, psig1050 Final Pressure, psig Measure Hydrogen partial pressure: 1250Calculated @ CAT, psi Hydrogen/Oil Ratio, SCFB 3000 Feed: 50/50 Blend ofLCO/MCO: FEED Inspections: API Gravity 7.7 Sulfur, PPM 9580 Nitrogen,PPM 1670 Refractive Index @ 20 C. 1.6068 Aromatic Carbon by ndM, % 86.9Distillation, D2887 10% @ 534 50% @ 666 90% @ 847 EP 1141Characterization Factor 10.26

Example 15

In this example, cetyl trimethylammonium bromide was used as thesurfactant. 0.97 g of cetyl trimethylammonium bromide was mixed with 100g DI water to yield a clear solution, followed by addition of 5 g ofconcentrated ammonia solution, 33.12 g of ammonium heptamolybdatetetrahydrate, and 8.1 of nickel sulfate hexahydrate, resulting in alight-blue mixture. This reaction mixture was heated to 70° C. underatmospheric pressure, and 92.04 g of ammonium sulfide solution (50 wt.%) was added slowly, over the course of 45 minutes. After that, themixture was heated with stirring for an additional 60 minutes.

The rest of the procedures and tests were similar to Example 1, exceptthe final product was sonicated for 10 min prior to testing. As noted inTable 1, the addition of the surfactant significantly improved thecatalytic activity, in terms of both HDN (327 ppm for Example 2 vs. 531ppm for Example 1) and HDS results (0.16 wt. % S for Example 2 vs. 0.22wt. % S for Example 1).

Example 16

Citric acid was used as the surfactant. In this example, 35 g of citricacid was dissolved in 100 g DI water to yield a clear solution, pH=1.4,followed by heating to 40° C. and addition of 31.9 g of ammoniumheptamolybdate tetrahydrate, pH=0.74 at 4 C. 8.1 of nickel sulfatehexahydrate was dissolved in 32 g of DI water, heated to 40° C. andadded to the ammonium heptamolybdate/citric acid solution. The color ofthe solution changed from pale yellow to light green to emerald green.This resulting mixture was heated to 70° C. under atmospheric pressure,pH=1.45 at 60° C. 91.97 g of ammonium sulfide solution (50 wt. %) wasadded slowly, over the course of 30 minutes. After that, the mixture washeated with stirring for an additional 60 minutes, pH=9 at 70° C. Therest of the procedures and tests were similar to Example 1.

Example 17 Vanadium/Molybdenum Catalyst with Citric Acid as thesurfactant, 12 wt. % Mo/6 wt. % V

35 g of citric acid was dissolved in 100 g DI water to yield a clearsolution, pH=1.4, followed by addition of 16.3 g of vanadyl sulfatehydrate, pH=0.6 at 21° C., and 17.65 g of ammonium heptamolybdatetetrahydrate, pH=0.7 at 21° C. The resulting mixture was heated to 70°C. under atmospheric pressure. 92 g of ammonium sulfide solution (50 wt.%) was added slowly, over the course of 30 minutes. After that, themixture was heated with stirring for an additional 80 minutes. The restof the procedures and tests were similar to Example 1.

Example 18

The catalytic activity of the catalyst precursors prepared in examples 1and 10 (as comparative example), 15, 16, and 17 were tested forHydrodenitrogenation (HDN), Hydrodesulfurization (HDS), as well as APIgravity change and Microcrystalline Carbon Residue (MCRT).

In this example, samples of the water-based catalyst precursors fromexamples 1, 10, 15-17 were subjected to batch transformation, by mixing3796 g of aqueous based precursor and 3000 g of vacuum gas oil (VGO) ina 3-gallon autoclave and heating to 400° F. under 400 psi of nitrogen.Then hydrogen was added with 32 SCF/h and the reduction was carried outuntil no H₂S was detected in the exit gas stream. This gave the finalcatalyst slurry was tested with medium cycle oil (MCO) and hydrogen in apressure test autoclave for HDN/HDS/API/MCRT activity. The results arepresented in Table 3.

TABLE 3 Feed no Feed + water catalyst no catalyst 1 15 16 17 5 APIgravity 7.5 10.5 13.3 13.8 13.4 12.3 14.7 HDN, ppm N 1730 1443 531 327705 780 402 HDS wt. % S 0.93 0.79 0.22 0.16 0.34 0.53 0.17 MCRT wt % — —0.98 — — — 0.91

Example 19

In this example, 5 g of maleic acid was dissolved in a mixture of 0.15 gof concentrated ammonia solution (28 wt. %) and 100 g deionized water.8.11 g of nickel sulfate hexahydrate was dissolved in 32 g of deionizedwater, and this solution was combined with the first one, yielding aclear emerald-green solution. 33.1 g of solid ammonium heptamolybdatetetrahydrate was added, resulting in a blue-green solution. This mixturewas heated to 70° C., and 92 g of 44 wt. % aqueous solution of ammoniumsulfide was added with stirring. The reaction mixture was heated at 70°C. for 1 hr. After that, the reaction mixture was removed from thereaction flask and evaporated to reduce the volume in half.

Activity of the resulting catalyst was tested as in Example 18 withother examples with the results being presented in Table 4 below. FIG.10 shows the PXRD spectrum of the product catalyst solids prepared inthis Example.

TABLE 4 Refractive API Nitrogen Sulfur Index @ 20 C. 60/6 wt ppm wt. %1.5870 10.4 1508.60 0.6087 1.5626 13.5 444.30 0.2446 1.5929 9.5 1568.500.5928

Example 20

Example 21 is a duplicate of Example 1, except that in addition to theammonium sulfide solution in water, 4.8 g of DEODS (diethanoldisulphide) containing 42.6% by weight sulphur mixed in 0.4 l of a 15%formic acid aqueous solution is added to the precipitate (emerald greensuspension).

Procedures and tests similar to Example 1 can be conducted to evaluatethe catalytic activity and life.

Example 22

Example 22 is a duplicate of Example 2, except that instead of DEODS, anequivalent sulfur stoichiometric quantity of a 50:50 by weight mixtureof flowers of sulphur and ditert. dodecyl polysulphide suspended in 0.4l of a 15% methyl formate solution in a white spirit is added to theprecipitate. Procedures and tests similar to Example 1 can be conductedto evaluate the catalytic activity and life.

Example 23 Mo Only Catalyst without any Promoter

33.12 g of ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄) wasdissolved in 100 g of water in a glass vessel fitted with an overheadmechanical stirrer, and 14.1 g of concentrated ammonia solution (28 wt.% NH₄OH in H₂O) was added. This mixture was heated to 70° C. underatmospheric pressure, and 101 g of ammonium sulfide ((NH₄)₂S) solutionin water (40-44 wt. %) was added slowly, over the course of 45 minutes.After that, the mixture was heated with stirring for an additional 60minutes. The volume of the reaction mixture was reduced in half on arotary evaporator. The resulting water-based catalyst precursor wastransformed to a final oil-based catalyst with medium cycle oil (MCO)and hydrogen in a pressure test autoclave in situ.

Example 24

The Mo-only catalyst of Example 23 was evaluated in converting a heavyoil feed consisting of highly aromatic FCC (“fluidized catalystcracking”) cycle oil with the following properties:

TABLE 5 Properties Feed API Gravity 2.9 Sulfur, PPM 1.01 Nitrogen, PPM1600 Refractive Index @ 20 C. 1.6405 MCRT, wt. % 5

The operating conditions were as follows: 725° F. for reactiontemperature, an equivalent of 3000 SCFB hydrogen to oil ratio, 1250 psigHydrogen partial pressure, 4 hours residence time, and catalyst to oilratio equal to 2 wt. % feed. The Mo-only catalyst of Example 23 wascompared with a Mo-only catalyst prepared without the transformationstep. The results are presented in Table 6.

TABLE 6 Refractive Nitrogen Run Index API wt. ppm Sulfur % MCRT %Comparative 1.5956 7.8 727 0.5677 1.32 example water based catalystInvention-oil 1.5860 8.8 694 0.5209 0.98 transformed catalyst

Example 25

Example 25 is a duplicate of Example 1, except that in addition to theammonium sulfide solution in water, 4.8 g of DEODS (diethanoldisulphide) containing 42.6% by weight sulphur mixed in 0.4 l of a 15%formic acid aqueous solution is added to the precipitate (emerald greensuspension).

Procedures and tests similar to Example 1 can be conducted to evaluatethe catalytic activity and life.

Example 26

Example 26 is a duplicate of Example 2, except that instead of DEODS, anequivalent sulfur stoichiometric quantity of a 50:50 by weight mixtureof flowers of sulphur and ditert. dodecyl polysulphide suspended in 0.4l of a 15% methyl formate solution in a white spirit is added to theprecipitate. Procedures and tests similar to Example 1 can be conductedto evaluate the catalytic activity and life.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. It isnoted that, as used in this specification and the appended claims, thesingular forms “a,” “an,” and “the,” include plural references unlessexpressly and unequivocally limited to one referent. As used herein, theterm “include” and its grammatical variants are intended to benon-limiting, such that recitation of items in a list is not to theexclusion of other like items that can be substituted or added to thelisted items.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to make and use the invention. The patentable scope is defined bythe claims, and may include other examples that occur to those skilledin the art. Such other examples are intended to be within the scope ofthe claims if they have structural elements that do not differ from theliteral language of the claims, or if they include equivalent structuralelements with insubstantial differences from the literal languages ofthe claims. All citations referred herein are expressly incorporatedherein by reference.

TABLE 2 Feed no Feed + water catalyst no catalyst 1 2 3 4 5 6 APIgravity 7.5 10.5 13.3 13.1 13.0 12.8 13.1 13.2 HDN, ppm N 1730 1443 531564 698 735 538 547 HDS wt. % S 0.93 0.79 0.22 0.24 0.19 0.21 0.22 0.23MCRT wt % — — 0.98 1.00 1.16 1.13 0.96 0.96 7 8 9 10 11 12 13 APIgravity 12.7 13.0 13.3 14.7 14.3 13.6 12.9 HDN, ppm N 634 404 507 402305 490 849 HDS wt. % S 0.29 0.17 0.17 0.21 0.15 0.28 0.29 MCRT wt %1.33 0.91 0.93 — — — —

1. A catalyst composition having a formula(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h),wherein M is at least one group VIB metal; L is at least a promotermetal selected from a non-noble Group VIII metal, a Group VIIIB metal, aGroup VIB metal, a Group IVB metal, and a Group IIB metal; t, u, v, w,x, y, z, each representing total charge for each of: M, L, S, C, H, Oand N, respectively; ta+ub+vd+we+xf+yg+zh=0; b>=0; 0=<b/a=<5,(a+0.5b)<=d<=(5b+2b), 0<=e<=11(a+b), 0<=f<=7(a+b), 0<=g<=5(a+b), 0<=h<=0.5(a+b), wherein the catalyst has an X-ray powder diffraction patternwith at least one broad diffraction peak at any of Bragg angles: 8 to18°, 32 to 40°, and 55 to 65° (from 0 to 70° 2θ scale) and wherein thecatalyst is prepared by a process in which at least at least a sulfuradditive is employed in the preparation of the catalyst.
 2. The catalystcomposition of claim 1, wherein the at least a sulfur additive isselected from the group of elemental sulfur, thiadiazoles, thio acids,thio amides, thiocyanates, thio esters, thiophenols, thiosemicarbazides,thioureas, mercapto alcohols, dialkyl sulfides, dihydroxyalkyl sulfides,diaryl sulfides, diaralkyl sulfides, dimethyl sulfoxides, diethanoldisulfide, tert-nonylpolysulfides, dimethyl sulphide, dimethyldisulphide, 2,2-dithiobis ethanol, and mixtures thereof.
 3. Thehydroprocessing catalyst composition of claim 2, wherein the at least asulfur additive is dimethyl disulphide in formic acid.
 4. Thehydroprocessing catalyst composition of claim 2, wherein the at least asulfur additive is dimethyl disulphide in a methyl formate organicsolution.
 5. The hydroprocessing catalyst composition of claim 2,wherein the at least a sulfur additive is sulphur in powder form mixedwith at least another sulphur compound.
 6. The hydroprocessing catalystcomposition of claim 3, wherein the at least a sulfur additive issulphur in powder form mixed with at least an organic polysulphide. 7.The catalyst of claim 1, wherein at least a surfactant is also employedin the preparation of the catalyst.
 8. The catalyst composition of claim7, wherein the surfactant is selected from N-containing organicadditives, P-containing organic additives, and mixtures thereof.
 9. Thecatalyst composition of claim 7, wherein the surfactant is selected fromthe group of aromatic amines, cyclic aliphatic amines, polycyclicaliphatic amines, and mixtures thereof.
 10. The catalyst composition ofclaim 7, wherein the surfactant is selected from the group ofhexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine,N,N-dimethyl-N′-ethylethylenediamine; amino alcohols, aminoalkoxy-silanes, and mixtures thereof.
 11. The catalyst composition ofclaim 1, wherein the surfactant is an organic carboxylic acidsurfactant.
 12. The catalyst composition of claim 1, wherein thesurfactant is water-soluble cationic amine selected from the group ofcetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride,dodecyl trimethyl ammonium amine, nonyl trimethyl ammonium chloride anddodecyl phenol quaternary amine soaps.
 13. The catalyst composition ofclaim 1, wherein the catalyst composition is substantially free ofpromoter metal L.
 14. The catalyst composition of claim 13, wherein b=0.15. The catalyst composition of claim 1, wherein the catalyst isprepared by: i) combining and reacting M with L to obtain anintermediate mixture; ii) sulfiding the intermediate mixture with asulfiding agent and the at least a sulfur additive to form a catalystprecursor; and iii) mixing the catalyst precursor with a hydrocarboncompound to form the hydroprocessing catalyst composition, wherein theat least a surfactant is added to any of the steps i), ii), and iii).16. The hydroprocessing catalyst composition of claim 15, wherein the atleast a sulfur additive is present in an amount ranging from 5 to 50 wt.% of the amount of sulfur in the sulfiding agent.
 17. The catalystcomposition of claim 1, wherein the catalyst is prepared by: i)sulfiding M with a sulfiding agent and the at least a sulfur additive toform a sulfided Group VI metal compound; ii) combining and reacting thesulfided Group VI metal compound with L to from a catalyst precursor;iii) mixing the catalyst precursor with a hydrocarbon compound to formthe hydroprocessing catalyst composition; wherein the at least asurfactant is added to any of the steps i), ii), and iii).
 18. Thecatalyst composition of claim 1, wherein the catalyst is prepared by: i)sulfiding M with a sulfiding agent and the at least a sulfur additive toform a sulfided Group VI metal compound; ii) sulfiding L with asulfiding agent to form a sulfided promoter metal compound; iii)combining and reacting the sulfided Group VI metal compound with thesulfided promoter metal compound to from a catalyst precursor; iv)mixing the catalyst precursor with a hydrocarbon compound to form thehydroprocessing catalyst composition; wherein the at least a surfactantis added to any of the steps i), ii), and iii).
 19. The catalystcomposition of claim 1, wherein the at least one diffraction peak isgreater than 2 degrees wide at ½ height.
 20. The catalyst composition ofclaim 1, wherein the at least one diffraction peak is at Bragg angle of8 to 18° (from 0 to 70° 2θ scale).
 21. The catalyst composition of claim20, wherein the diffraction peak at Bragg angle 8 to 18° (from 0 to 70°2θ scale) is greater than 2 degrees wide at ½ height.
 22. The catalystcomposition of claim 21, wherein the diffraction peak at Bragg angle 8to 18° (from 0 to 70° 2θ scale) is greater than 5 degrees wide at ½height.
 23. The catalyst composition of claim 1, having a first broaddiffraction peak at Bragg angle of 8 to 18° (from 0 to 70°2θ scale) anda second first broad diffraction peak at Bragg angle of 32 to 40° (from0 to 70° 2θ scale).
 24. The catalyst composition of claim 1, wherein thecatalyst has a median particle size of 0.0005 to 1000 microns.
 25. Thecatalyst composition of claim 1, wherein the catalyst has an averageparticle size of 0.3 to 20 μm.
 26. The catalyst composition of claim 1,wherein the catalyst has a pore volume of 0.05-5 ml/g as determined bynitrogen adsorption.
 27. The catalyst composition of claim 1, whereinthe catalyst has a pore volume of 0.1-4 ml/g as determined by nitrogenadsorption.
 28. The catalyst composition of claim 1, wherein thecatalyst has a surface area of at least 5 m²/g.
 29. The catalystcomposition of claim 1, wherein M is selected from molybdenum, tungsten,and mixtures thereof and L is selected from nickel, cobalt, and mixturethereof.
 30. The catalyst composition of claim 1, wherein L is selectedfrom nickel, cobalt and combinations thereof, the catalyst is of theformula(M)_(a)(Ni_(z)Co_(1-z))_(b)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h), andwherein 0<z<1.
 31. The catalyst composition of claim 1, wherein M isselected from molybdenum, tungsten, and combinations thereof, thecatalyst is of the formula(Mo_(z)W_(1-z))_(a)(L)_(b)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h), andwherein 0<z<1.
 32. The catalyst composition of claim 1, wherein L isselected from Ni, Co, Fe, Zn, Cr, Ti, and combinations thereof, thecatalyst is of the formula(M)_(a)(Ni_(z)Co_(z)Fe_(z″)Zn_(z*)Cr_(z*′)Ti_(z*″))_(b)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h),and wherein 0≦z, z′, z″, z*, z*′, z*″ and (z+z′+z″+z*+z*′+z*″=1.
 33. Thecatalyst composition of claim 1, wherein the catalyst further comprisesa refractory oxide material which comprises 50 wt. % or more titania, onoxide basis.
 34. The catalyst composition of claim 1, wherein thecatalyst is added to a heavy oil feedstock in an amount sufficient toprovide 100 to 2000 ppm of active group VIB metal.